The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for ...The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.展开更多
Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets ...Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets vertically aligned on activated carbon cloth substrate,which was in situ transformed from Co-metal-organic framework materials nano-columns by a simple ion exchange process at room temperature.Due to the amorphous and vertically aligned ultrathin structure of NiCo-LDH,the NiCo-LDH/activated carbon cloth composites present high areal capacities of 3770 and 1480 mF cm^(-2)as cathode and anode at 2 mA cm^(-2),and 79.5%and 80%capacity have been preserved at 50 mA cm^(-2).In the meantime,they all showed excellent cycling performance with negligible change after>10000 cycles.By fabricating them into an asymmetric supercapacitor,the device achieves high energy densities(5.61 mWh cm^(-2)and 0.352 mW cm^(-3)).This work provides an innovative strategy for simplifying the design of supercapacitors as well as providing a new understanding of improving the rate capabilities/cycling stability of NiCo-LDH materials.展开更多
As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the ...As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp3-C/sp2-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.展开更多
The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large en...The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large energy consumption,resulting in low throughputs and efficiency.In our contribution,a novel synthesis method is proposed,involving the formation of HC nanosheets(NS-CNs)within minutes by creating an anoxic environment through flame combustion and further introducing sulfur and nitrogen sources to achieve heteroatom doping.The effect of heterogeneous element doping on the microstructure of HC is quantitatively analyzed by high-resolution transmission electron microscopy and image processing technology.Combined with density functional theory calculation,it is verified that the functionalized HC exhibits stronger Na^(+)adsorption ability,electron gain ability,and Na^(+) migration ability.As a result,NS-CNs as SIB anodes provide an ultrahigh reversible capacity of 542.7mAh g^(-1) at 0.1Ag^(-1),and excellent rate performance with a reversible capacity of 236.4mAh g^(-1) at 2Ag^(-1) after 1200 cycles.Furthermore,full cell assembled with NS-CNs as the can present 230mAh g^(-1) at 0.5Ag^(-1) after 150 cycles.Finally,in/ex situ techniques confirm that the excellent sodium storage properties of NS-CNs are due to the construction of abundant active sites based on the novel synthesis method for realizing the reversible adsorption of Na^(+).This work provides a novel strategy to develop novel carbons and gives deep insights for the further investigation of facile preparation methods to develop high-performance carbon anodes for alkali-ion batteries.展开更多
Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)...Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.展开更多
As electromagnetic technology advances and demand for electronic devices grows,concerns about electromagnetic pollution intensify.This has spurred focused research on innovative electromagnetic absorbers,particularly ...As electromagnetic technology advances and demand for electronic devices grows,concerns about electromagnetic pollution intensify.This has spurred focused research on innovative electromagnetic absorbers,particularly chalcogenides,noted for their superior absorption capabilities.In this study,we successfully synthesize 3R–TaS_(2)nanosheets using a straightforward calcination method for the first time.These nanosheets exhibit significant absorption capabilities in both the C-band(4–8 GHz)and Ku-band(12–18 GHz)frequency ranges.By optimizing the calcination process,the complex permittivity of TaS_(2)is enhanced,specifically for those synthesized at 1000℃for 24 h.The nanosheets possess dual-band absorption properties,with a notable minimum reflection loss(RLmin)of41.4 dB in the C-band,and an average absorption intensity exceeding 10 dB in C-and Ku-bands,in the absorbers with a thickness of 5.6 mm.Additionally,the 3R–TaS_(2)nanosheets are demonstrated to have an effective absorption bandwidth of 5.04 GHz(3.84–8.88 GHz)in the absorbers with thicknesses of 3.5–5.5 mm.The results highlight the multiple reflection effects in 3R–TaS_(2)as caused by their stacked structures,which could be promising low-frequency absorbers.展开更多
Liquid-phase exfoliation was employed to synthesize Sr_(2)Nb_(3)O_(10) perovskite nanosheets with thicknesses down to 1.76 nm.Transmission electron microscopy(TEM),atomic force microscope(AFM),X-ray photoelectron spec...Liquid-phase exfoliation was employed to synthesize Sr_(2)Nb_(3)O_(10) perovskite nanosheets with thicknesses down to 1.76 nm.Transmission electron microscopy(TEM),atomic force microscope(AFM),X-ray photoelectron spectrometer(XPS),and other characterization techniques were used to evaluate the atomic structure and chemical composition of the exfoliated nanosheets.A UV photodetector based on individual Sr_(2)Nb_(3)O_(10) nanosheets was prepared to demonstrate the application of an ultraviolet(UV) photodetector.The UV photodetector exhibited outstanding photocurrent and responsivity with a responsivity of 3×10^(5) A·W^(-1) at 5 V bias under 280 nm illumination,a photocurrent of 60 nA,and an on/off ratio of 3×10^(2).展开更多
As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,...As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic performance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessible holey Fe_(2)O_(3) moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O_(2) adsorption and dissociation on Fe_(2)O_(3) hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe_(2)O_(3) active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe_(2)O_(3)@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interactions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.展开更多
Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance...Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance electrocatalysts.Herein,we elaborately design and develop strongly coupled nanosheets composed of Ag nanoparticles and Sn-SnO_(2) grains,designated as Ag/Sn-SnO_(2) nanosheets(NSs),which possess optimized electronic structure,high electrical conductivity,and more accessible sites.As a result,such a catalyst exhibits unprecedented catalytic performance toward CO_(2)-to-formate conversion with near-unity faradaic efficiency(≥90%),ultrahigh partial current density(2,000 mA cm^(−2)),and superior long-term stability(200 mA cm^(−2),200 h),surpassing the reported catalysts of CO_(2) electroreduction to formate.Additionally,in situ attenuated total reflection-infrared spectra combined with theoretical calculations revealed that electron-enriched Sn sites on Ag/Sn-SnO_(2)NSs not only promote the formation of*OCHO and alleviate the energy barriers of*OCHO to*HCOOH,but also impede the desorption of H*.Notably,the Ag/Sn-SnO_(2)NSs as the cathode in a membrane electrode assembly with porous solid electrolyte layer reactor can continuously produce~0.12 M pure HCOOH solution at 100 mA cm^(−2)over 200 h.This work may inspire further development of advanced electrocatalysts and innovative device systems for promoting practical application of producing liquid fuels from CO_(2).展开更多
The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to C...The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.展开更多
The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces c...The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.展开更多
Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheet...Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheets(SFe-DMNs)were prepared based on the high-throughput density functional theory(DFT)calculation screening.Due to the synergistic effect between Fe atom and MoS_(2)and optimized intermediate binding energy,the SFe-DMNs could deliver outstanding activity for both HER and OER.When assembled into a two-electrode electrolytic cell,the SFe-DMNs could achieve the current density of 50 mA cm^(-2)at a low cell voltage of 1.55 V under neutral condition.These results not only confirmed the effectiveness of high-throughput screening,but also revealed the excellent activity and thus the potential applications in fuel cells of SFe-DMNs.展开更多
Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely li...Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.展开更多
By virtue of the flexibility and safety, polyethylene oxide(PEO) based electrolytes are regarded as an appealing candidate for all-solid-state lithium batteries. However, their application is limited by the poor ionic...By virtue of the flexibility and safety, polyethylene oxide(PEO) based electrolytes are regarded as an appealing candidate for all-solid-state lithium batteries. However, their application is limited by the poor ionic conductivity at room temperature, narrow electrochemical stability window and uncontrolled growth of lithium dendrite. To alleviate these problems, we introduce the ultrathin graphitic carbon nitride nanosheets(GCN) as advanced nanofillers into PEO based electrolytes(GCN-CPE). Benefiting from the high surface area and abundant surface N-active sites of GCN, the GCN-CPE displays decreased crystallinity and enhanced ionic conductivity. Meanwhile, Fourier transform infrared and chronoamperometry studies indicate that GCN can facilitate Li+migration in the composite electrolyte. Additionally, the GCN-CPE displays an extended electrochemical window compared with PEO based electrolytes. As a result, Li symmetric battery assembled with GCN-CPE shows a stable Li plating/stripping cycling performance, and the all-solid-state Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622) batteries using GCN-CPE exhibit satisfactory cyclability and rate capability in a voltage range of 3-4.2 V at 30 ℃.展开更多
Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the the...Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.展开更多
Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especial...Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.展开更多
A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidati...A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidation of biomass-derived furfuryl alcohol(FFA)into furoic acid(FurAc)catalyzed by the electrodeposited non-precious NiFe microflowers was successfully reached under the low temperature and ambient pressure.The 3D hierarchical NiFe microflowers assembled from ultrathin nanosheets were controllably synthesized by the electrodeposition method and uniformly grown on carbon fiber paper(CFP).Electrochemical analysis confirmed that NiFe nanosheets more preferred in the selective oxidation of FFA(FFAOR)than oxygen evolution reaction(OER).The linear sweep voltammetry(LSV)in FFAOR displayed a clear decrease towards lower potential,resulting in 30 mV reduction of overpotential at 20 mA cm^(-2) compared with that of OER.The optimal catalyst Ni_(1)Fe_(2) nanosheets exhibited the highest selectivity of FurAc(94.0%)and 81.4%conversion of FFA within 3 h.Besides,the influence of various reaction parameters on FFAOR was then explored in details.After that,the reaction pathway was investigated and rationally proposed.The outstanding performance for FFAOR can be ascribed to the unique structure of 3D flower-like NiFe nanosheets and oxygen vacancies,resulting in large exposure of active sites,faster electron transfer and enhanced adsorption of reactants.Our findings highlight a facile and convenient mean with a promising green future,which is promising for processing of various biomass-derived platform chemicals into value-added products.展开更多
The conversion of CO_(2)into value-added chemicals coupled with the storage of intermittent renewable electricity is attractive.CuO nanosheets with an average size and thickness of~30 and~20 nm have been developed,whi...The conversion of CO_(2)into value-added chemicals coupled with the storage of intermittent renewable electricity is attractive.CuO nanosheets with an average size and thickness of~30 and~20 nm have been developed,which are in situ reduced into Cu nanosheets during electrochemical CO_(2)reduction reaction(ECO_(2)RR).The derived Cu nanosheets demonstrate much higher selectivity for C2H4production than commercial CuO derived Cu powder,with an optimum Faradaic efficiency of 56.2%and a partial current density of C_(2)H_(4)as large as 171.0 mA cm^(-2)in a gas diffusion flow cell.The operando attenuated total reflectance-Fourier transform infrared spectra measurements and density functional theory simulations illustrate that the high activity and selectivity of Cu nanosheets originate from the edge sites on Cu nanosheets with a coordinate number around 5(4–6),which facilitates the formation of^(*)CHO rather than^(*)COH intermediate,meanwhile boosting the C-C coupling reaction of^(*)CO and^(*)CHO intermediates,which are the critical steps for C_(2)H_(4)formation.展开更多
The introduction of bifunctional groups into low-cost adsorbents for selective adsorption of Ag(I) through synergistic effect will have a profound impact on the recovery of precious metals. Organo silica nanosheets(or...The introduction of bifunctional groups into low-cost adsorbents for selective adsorption of Ag(I) through synergistic effect will have a profound impact on the recovery of precious metals. Organo silica nanosheets(organo-Si NSs) functionalized by series of azole derivatives(2-mercaptoimidazole(MI), 2-mercaptobenzimidazole(MBT) and 1H-1,2,4-triazole-3-thiol(MTT)), are fabricated and employed for selective removal of Ag(I). The structures of the organo-Si NSs are investigated using several characterization methods. The results of batch adsorption experiments display that the maximum adsorption amounts are 70.3, 103.2 and 139.5 mg·g^(-1) on MI-Si NSs, MBI-Si NSs and MTT-Si NSs for Ag(I) ions, and reach rapid equilibrium within 10–30 min. The adsorption processes are chemisorption and fit pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Notably, MTT-Si NSs is greatly selective for Ag(I) in multicomponent system, and the distribution coefficient value of Ag(I) ions reaches 2331.26 ml·g^(-1). The reusability of organo-Si NSs is verified by four cycles of regeneration tests with 0.1 mol·L^(-1) HNO_(3) as the eluent. A combination of experimental, structural along with theoretical analysis is conducted to proclaim the structure-adsorptivity relationship:(i) The adsorption mechanisms are attributed to complexation.(ii) The amino group and sulfhydryl group of MTT-Si NSs as well as MBISi NSs may have synergistic impacts on Ag(I) capture.(iii) The differences in adsorption behavior and selectivity of the three organo-Si NSs are mainly related to the form of function groups, charge density and steric hindrance of adsorbent. This work not only sheds light on the promise of functionalized organo-Si NSs for the rapid and selective removal/enrichment of Ag(I) ions in complex water systems,but also provides new insights for designing cost-effective Si NSs-based adsorbents.展开更多
Janus amphiphilic polymer nanosheets(JAPNs)with anisotropic morphology and distinctive perfor-mance have aroused widespread interest.However,due to the difficulty in synthesis and poor dispersion stability,JAPNs have ...Janus amphiphilic polymer nanosheets(JAPNs)with anisotropic morphology and distinctive perfor-mance have aroused widespread interest.However,due to the difficulty in synthesis and poor dispersion stability,JAPNs have been scarcely reported in the field of enhancing oil recovery(EOR).Herein,a kind of organic-based flexible JAPNs was prepared by paraffin emulsion methods.The lateral sizes of JAPNs were ranging from hundreds of nanometers to several micrometers and the thickness was about 3 nm.The organic-based nanosheets were equipped with remarkably flexible structures,which could improve their injection performance.The dispersion and interfacial properties of JAPNs were studied systematically.By modification of crosslinking agent containing multiple amino groups,the JAPNs had excellent hydro-philicity and salt resistance compared with conventional inorganic or composite nanosheets.The settling time of nanosuspension with NaCl and CaCl_(2) at a low salinity of 1000 mg/L was over 240 h.The value could also remain 124 h under the salinity of 10,000 mg/L NaCl.With the dual functionalities of Janus amphiphilic nature and nanoparticles'Pickering effect,JAPNs could change rock wettability and form emulsions as"colloidal surfactants",In particular,a new technology called optical microrheology was pioneered to explore the destabilization state of nanosuspensions for the first time.Since precipitation lagged behind aggregation,especially for stable suspension systems,the onset of the unstable behavior was difficult to be detected by conventional methods,which should be the indicator of reduced effec-tiveness for nanofluid products.In addition,the oil displacement experiments demonstrated that the JAPNs could enhance oil recovery by 17.14%under an ultra-low concentration of 0.005%and were more suitable for low permeability cores.The findings can help for a better understanding of the material preparation of polymer nanosheets.We also hope that this study could shed more light on the nano-flooding technology for EOR.展开更多
基金supported by the National Natural Science Foundation of China(22108238,21878259)the Zhejiang Provincial Natural Science Foundation of China(LR18B060001)+5 种基金Anhui Provincial Natural Science Founda-tion(1908085QB68)the Natural Science Foundation of the Anhui Higher Education Institutions of China(KJ2020A0275)Major Science and Technology Project of Anhui Province(201903a05020055)Foundation of Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology(ZJKL-ACEMT-1802)China Postdoctoral Science Foundation(2019M662060,2020T130580)Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110).
文摘The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.
基金the funding from Natural Science Foundation of China(No.52003163)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515010670)+1 种基金Science and Technology Innovation Commission of Shenzhen(Nos.KQTD20170810105439418 and 20200812112006001)NTUT-SZU Joint Research Program(Nos.2022005 and 2022015)
文摘Developing a simple scalable method to fabricate electrodes with high capacity and wide voltage range is desired for the real use of electrochemical supercapacitors.Herein,we synthesized amorphous NiCo-LDH nanosheets vertically aligned on activated carbon cloth substrate,which was in situ transformed from Co-metal-organic framework materials nano-columns by a simple ion exchange process at room temperature.Due to the amorphous and vertically aligned ultrathin structure of NiCo-LDH,the NiCo-LDH/activated carbon cloth composites present high areal capacities of 3770 and 1480 mF cm^(-2)as cathode and anode at 2 mA cm^(-2),and 79.5%and 80%capacity have been preserved at 50 mA cm^(-2).In the meantime,they all showed excellent cycling performance with negligible change after>10000 cycles.By fabricating them into an asymmetric supercapacitor,the device achieves high energy densities(5.61 mWh cm^(-2)and 0.352 mW cm^(-3)).This work provides an innovative strategy for simplifying the design of supercapacitors as well as providing a new understanding of improving the rate capabilities/cycling stability of NiCo-LDH materials.
文摘As by-products of petroleum refining,heavy oils are characterized by a high carbon content,low cost and great variability,making them competitive precursors for the anodes of potassium ion batteries(PIBs).However,the relationship between heavy oil composition and potassium storage performance remains unclear.Using heavy oils containing distinct chemical groups as the carbon source,namely fluid catalytic cracking slurry(FCCS),petroleum asphalt(PA)and deoiled asphalt(DOA),three carbon nanosheets(CNS)were prepared through a molten salt method,and used as the anodes for PIBs.The composition of the heavy oil determines the lamellar thicknesses,sp3-C/sp2-C ratio and defect concentration,thereby affecting the potassium storage performance.The high content of aromatic hydrocarbons and moderate amount of heavy component moieties in FCCS produce carbon nanosheets(CNS-FCCS)that have a smaller layer thickness,larger interlayer spacing(0.372 nm),and increased number of folds than in CNS derived from the other three precursors.These features give it faster charge/ion transfer,more potassium storage sites and better reaction kinetics.CNS-FCCS has a remarkable K^(+)storage capacity(248.7 mAh g^(-1) after 100 cycles at 0.1 A g^(-1)),long cycle lifespan(190.8 mAh g^(-1) after 800 cycles at 1.0 A g^(-1))and excellent rate capability,ranking it among the best materials for this application.This work sheds light on the influence of heavy oil composition on carbon structure and electrochemical performance,and provides guidance for the design and development of advanced heavy oil-derived carbon electrodes for PIBs.
基金supported by the National Natural Science Foundation of China (Grant Nos.51872236,52072307)MOE SUTD Kickstarter Innitiative (SKI 2021_02_16).
文摘The unique structural features of hard carbon(HC)make it a promising anode candidate for sodium-ion batteries(SIB).However,traditional methods of preparing HC require special equipment,long reaction times,and large energy consumption,resulting in low throughputs and efficiency.In our contribution,a novel synthesis method is proposed,involving the formation of HC nanosheets(NS-CNs)within minutes by creating an anoxic environment through flame combustion and further introducing sulfur and nitrogen sources to achieve heteroatom doping.The effect of heterogeneous element doping on the microstructure of HC is quantitatively analyzed by high-resolution transmission electron microscopy and image processing technology.Combined with density functional theory calculation,it is verified that the functionalized HC exhibits stronger Na^(+)adsorption ability,electron gain ability,and Na^(+) migration ability.As a result,NS-CNs as SIB anodes provide an ultrahigh reversible capacity of 542.7mAh g^(-1) at 0.1Ag^(-1),and excellent rate performance with a reversible capacity of 236.4mAh g^(-1) at 2Ag^(-1) after 1200 cycles.Furthermore,full cell assembled with NS-CNs as the can present 230mAh g^(-1) at 0.5Ag^(-1) after 150 cycles.Finally,in/ex situ techniques confirm that the excellent sodium storage properties of NS-CNs are due to the construction of abundant active sites based on the novel synthesis method for realizing the reversible adsorption of Na^(+).This work provides a novel strategy to develop novel carbons and gives deep insights for the further investigation of facile preparation methods to develop high-performance carbon anodes for alkali-ion batteries.
基金supported by the National Natural Science Foundation of China(21571038,22035004)the Education Department of Guizhou Province(2021312)+2 种基金the Foundation of Guizhou Province(2019-5666)the National Key R&D Program of China(2017YFA0700101)the State Key Laboratory of Physical Chemistry of Solid Surfaces(Xiamen University,202009)。
文摘Surface/interface engineering of a multimetallic nanostructure with diverse electrocatalytic properties for direct liquid fuel cells is desirable yet challenging.Herein,using visible light,a class of quaternary Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)ultrathin nanosheets is fabricated and used as high-performance anode electrocatalysts for formic acid-/alcohol-air fuel cells.The modified electronic structure of Pt,enhanced hydroxyl adsorption,and abundant exterior defects afford Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C high intrinsic anodic electrocatalytic activity to boost the power densities of direct formic acid-/methanol-/ethanol-/ethylene glycol-/glycerol-air fuel cells,and the corresponding peak power density of Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C is respectively 129.7,142.3,105.4,124.3,and 128.0 mW cm^(-2),considerably outperforming Pt/C.Operando in situ Fourier transform infrared reflection spectroscopy reveals that formic acid oxidation on Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)/C occurs via a CO_(2)-free direct pathway.Density functional theory calculations show that the presence of Ag,Bi,and Te in Pt_(1)Ag_(0.1)Bi_(0.16)Te_(0.29)suppresses CO^(*)formation while optimizing dehydrogenation steps and synergistic effect and modified Pt effectively enhance H_(2)O dissociation to improve electrocatalytic performance.This synthesis strategy can be extended to 43 other types of ultrathin multimetallic nanosheets(from ternary to octonary nanosheets),and efficiently capture precious metals(i.e.,Pd,Pt,Rh,Ru,Au,and Ag)from different water sources.
基金supported by the National Natural Science Foundation of China(52372289,52102368,52072192 and 51977009)Regional Joint Fund for Basic Research and Applied Basic Research of Guangdong Province(No.2020A1515110905)+1 种基金Guangdong Special Fund for key Areas(20237DZX3042)Shenzhen Stable Support Project.
文摘As electromagnetic technology advances and demand for electronic devices grows,concerns about electromagnetic pollution intensify.This has spurred focused research on innovative electromagnetic absorbers,particularly chalcogenides,noted for their superior absorption capabilities.In this study,we successfully synthesize 3R–TaS_(2)nanosheets using a straightforward calcination method for the first time.These nanosheets exhibit significant absorption capabilities in both the C-band(4–8 GHz)and Ku-band(12–18 GHz)frequency ranges.By optimizing the calcination process,the complex permittivity of TaS_(2)is enhanced,specifically for those synthesized at 1000℃for 24 h.The nanosheets possess dual-band absorption properties,with a notable minimum reflection loss(RLmin)of41.4 dB in the C-band,and an average absorption intensity exceeding 10 dB in C-and Ku-bands,in the absorbers with a thickness of 5.6 mm.Additionally,the 3R–TaS_(2)nanosheets are demonstrated to have an effective absorption bandwidth of 5.04 GHz(3.84–8.88 GHz)in the absorbers with thicknesses of 3.5–5.5 mm.The results highlight the multiple reflection effects in 3R–TaS_(2)as caused by their stacked structures,which could be promising low-frequency absorbers.
基金Funded by the National Natural Science Foundation of China(Nos.51872214 and 52172124)the Fundamental Research Funds for the Central Universities(WUT:2021Ⅲ019JC and 2018Ⅲ041GX)。
文摘Liquid-phase exfoliation was employed to synthesize Sr_(2)Nb_(3)O_(10) perovskite nanosheets with thicknesses down to 1.76 nm.Transmission electron microscopy(TEM),atomic force microscope(AFM),X-ray photoelectron spectrometer(XPS),and other characterization techniques were used to evaluate the atomic structure and chemical composition of the exfoliated nanosheets.A UV photodetector based on individual Sr_(2)Nb_(3)O_(10) nanosheets was prepared to demonstrate the application of an ultraviolet(UV) photodetector.The UV photodetector exhibited outstanding photocurrent and responsivity with a responsivity of 3×10^(5) A·W^(-1) at 5 V bias under 280 nm illumination,a photocurrent of 60 nA,and an on/off ratio of 3×10^(2).
基金supported by the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(MSIT)(RS2023-00235596)and ERC Center(2022R1A5A1033719)。
文摘As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic performance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessible holey Fe_(2)O_(3) moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O_(2) adsorption and dissociation on Fe_(2)O_(3) hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe_(2)O_(3) active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe_(2)O_(3)@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interactions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.
基金the National Science Fund for Distinguished Young Scholars(Grant No.52125103)the National Natural Science Foundation of China(Grant Nos.52301232,52071041,12074048,and 12147102)China Postdoctoral Science Foundation(Grant No.2022M720552).
文摘Electrocatalytic reduction of CO_(2) converts intermittent renewable electricity into value-added liquid products with an enticing prospect,but its practical application is hampered due to the lack of high-performance electrocatalysts.Herein,we elaborately design and develop strongly coupled nanosheets composed of Ag nanoparticles and Sn-SnO_(2) grains,designated as Ag/Sn-SnO_(2) nanosheets(NSs),which possess optimized electronic structure,high electrical conductivity,and more accessible sites.As a result,such a catalyst exhibits unprecedented catalytic performance toward CO_(2)-to-formate conversion with near-unity faradaic efficiency(≥90%),ultrahigh partial current density(2,000 mA cm^(−2)),and superior long-term stability(200 mA cm^(−2),200 h),surpassing the reported catalysts of CO_(2) electroreduction to formate.Additionally,in situ attenuated total reflection-infrared spectra combined with theoretical calculations revealed that electron-enriched Sn sites on Ag/Sn-SnO_(2)NSs not only promote the formation of*OCHO and alleviate the energy barriers of*OCHO to*HCOOH,but also impede the desorption of H*.Notably,the Ag/Sn-SnO_(2)NSs as the cathode in a membrane electrode assembly with porous solid electrolyte layer reactor can continuously produce~0.12 M pure HCOOH solution at 100 mA cm^(−2)over 200 h.This work may inspire further development of advanced electrocatalysts and innovative device systems for promoting practical application of producing liquid fuels from CO_(2).
基金Natural Science Foundation of Shandong Province,Grant/Award Number:ZR2022MB106national training program of innovation and entrepreneurship for undergraduates,Grant/Award Number:202210424099National Natural Science Foundation of China,Grant/Award Numbers:21601067,21701057,21905147。
文摘The photocatalytic conversion of CO_(2)into solar‐powered fuels is viewed as a forward‐looking strategy to address energy scarcity and global warming.This work demonstrated the selective photoreduction of CO_(2)to CO using ultrathin Bi_(12)O_(17)Cl_(2)nanosheets decorated with hydrothermally synthesized bismuth clusters and oxygen vacancies(OVs).The characterizations revealed that the coexistences of OVs and Bi clusters generated in situ contributed to the high efficiency of CO_(2)–CO conversion(64.3μmol g^(−1)h^(−1))and perfect selectivity.The OVs on the facet(001)of the ultrathin Bi_(12)O_(17)Cl_(2)nanosheets serve as sites for CO_(2)adsorption and activation sites,capturing photoexcited electrons and prolonging light absorption due to defect states.In addition,the Bi‐cluster generated in situ offers the ability to trap holes and the surface plasmonic resonance effect.This study offers great potential for the construction of semiconductor hybrids as multiphotocatalysts,capable of being used for the elimination and conversion of CO_(2)in terms of energy and environment.
基金partial support from the Jiujiang Research Institute at Xiamen University.
文摘The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.
基金supported by the Research Funds of Institute of Zhejiang University-Quzhou(IZQ2023RCZX032)the Natural Science Foundation of Guangdong Province(2022A1515010185)+1 种基金the Fundamental Research Funds for the Central Universities(FRF-TP-20-005A3)partially supported by the Special Funds for Postdoctoral Research at Tsinghua University(100415017)。
文摘Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheets(SFe-DMNs)were prepared based on the high-throughput density functional theory(DFT)calculation screening.Due to the synergistic effect between Fe atom and MoS_(2)and optimized intermediate binding energy,the SFe-DMNs could deliver outstanding activity for both HER and OER.When assembled into a two-electrode electrolytic cell,the SFe-DMNs could achieve the current density of 50 mA cm^(-2)at a low cell voltage of 1.55 V under neutral condition.These results not only confirmed the effectiveness of high-throughput screening,but also revealed the excellent activity and thus the potential applications in fuel cells of SFe-DMNs.
基金supported by the National Natural Science Foundation of China(11872171 and 22209037)the Project on Excellent Post-graduate Dissertation of Hohai University。
文摘Although metallic rhodium(Rh)is regarded as a promising platinum-alternative anode catalyst of direct methanol fuel cell(DMFC),the conventional"particle-to-face"contact model between Rh and matrix largely limits the overall electrocatalytic performance due to their insufficient cooperative effects.Herein,we report a controllable and robust heterointerface engineering strategy for the bottom-up fabrication of rhombic Rh nanosheets in situ confined on Ti_3C_(2)T_x MXene nanolamellas(Rh NS/MXene)via a convenient stereoassembly process.This unique design concept gives the resulting 2D/2D Rh NS/MXene heterostructure intriguing textural features,including large accessible surface areas,strong"face-toface"interfacial interactions,homogeneous Rh nanosheet distribution,ameliorative electronic structure,and high electronic conductivity.As a consequence,the as-prepared Rh NS/MXene nanoarchitectures exhibit exceptional electrocatalytic methanol oxidation properties in terms of a large electrochemically active surface area of 126.2 m~2 g_(Rh)~(-1),a high mass activity of 1056.9 mA mg_(Rh)-~1,and a long service life,which significantly outperform those of conventional particle-shaped Rh catalysts supported by carbon black,carbon nanotubes,reduced graphene oxide,and MXene matrixes as well as the commercial Pt nanoparticle/carbon black and Pd nanoparticle/carbon black catalysts with the same noble metal loading amount.Density functional theory calculations further demonstrate that the direct electronic interaction at the well-contacted 2D/2D heterointerfaces effectively enhances the adsorption energy of Rh nanosheets and induces a left shift of the d-band center,thereby making the Rh NS/MXene configuration suffer less from CO poisoning.This work highlights the importance of rational heterointerface design in the construction of advanced noble metal/MXene electrocatalysts,which may provide new avenues for developing the next-generation DMFC devices.
基金the National Natural Science Foundation of China (22178120)Guangdong Natural Science Funds for Distinguished Young Scholar (2017A030306022)Guangzhou Technology Project (202002030164)。
文摘By virtue of the flexibility and safety, polyethylene oxide(PEO) based electrolytes are regarded as an appealing candidate for all-solid-state lithium batteries. However, their application is limited by the poor ionic conductivity at room temperature, narrow electrochemical stability window and uncontrolled growth of lithium dendrite. To alleviate these problems, we introduce the ultrathin graphitic carbon nitride nanosheets(GCN) as advanced nanofillers into PEO based electrolytes(GCN-CPE). Benefiting from the high surface area and abundant surface N-active sites of GCN, the GCN-CPE displays decreased crystallinity and enhanced ionic conductivity. Meanwhile, Fourier transform infrared and chronoamperometry studies indicate that GCN can facilitate Li+migration in the composite electrolyte. Additionally, the GCN-CPE displays an extended electrochemical window compared with PEO based electrolytes. As a result, Li symmetric battery assembled with GCN-CPE shows a stable Li plating/stripping cycling performance, and the all-solid-state Li/LiNi_(0.6)Co_(0.2)Mn_(0.2)O_(2)(NCM622) batteries using GCN-CPE exhibit satisfactory cyclability and rate capability in a voltage range of 3-4.2 V at 30 ℃.
基金the National Natural Science Foundation of China(Grant No.21975227)the Found of National defence Sci&Tech Laboratory(Grant No.6142602210306)。
文摘Energetic molecular perovskites have attracted widespread attention in the fields of energy materials due to their high detonation performance.In this work,we reported the effect of MgCo_(2)O_(4) nanosheets on the thermal decomposition of ammonium perchlorate(NH_(4)ClO_(4),AP)-based energetic molecular perovskites(AP-based energetic molecular perovskites).The morphology and structure of the MgCo_(2)O_(4) nanosheets were characterized.And their catalytic effect on the thermal decomposition of AP-based energetic molecular perovskites(H_2pz)[NH_(4)(ClO_(4))_(3)](PAP-4),(H_2dabco)[NH_(4)(ClO_(4))_(3)](DAP-4),(H_2mpz)[NH_(4)(ClO_(4))_(3)](PAP-M_(4)),and (H_2hpz)[NH_(4)(ClO_(4))_(3)](PAP-H_(4)) was analyzed.The results showed that MgCo_(2)O_(4) nanosheets had excellent intrinsically catalytic performance towards enhancing the thermal decomposition of AP-based energetic molecular perovskites.After adding MgCo_(2)O_(4) nanosheets,the thermal decomposition peak temperatures of PAP-4,DAP-4,PAP-M_(4),and PAP-H_(4) had been reduced by35.7℃,48.4℃,37.9℃,and 43.6℃,respectively.And the activation energy(Ea)of the thermal decomposition of AP-based energetic molecular perovskites had been reduced,the Eaof PAP-H_(4) decreased by 46.4 kJ/mol at most among them.The catalytic mechanism of MgCo_(2)O_(4) nanosheets for AP-based energetic molecular perovskites is analyzed.This work provides a reference for the future application of AP-based energetic molecular perovskites.
基金supported by National Natural Science Foundation of China(Nos.U20A20246,51872108)the Fundamental Research Funds for the Central Universities(Nos.30106200463 and CCNU20TS006)Graduate Education Innovation Grant from Central China Normal University(No.2020CXZZ101).
文摘Manganese-based cathode materials are considered as a promising candidate for rechargeable aqueous zinc-ion batteries(ZIBs).Suffering from poor conductive and limited structure tolerance,various carbon matrix,especially N-doped carbon,were employed to incorporate with MnO_(2)for greatly promoted electrochemical performances.However,the related underlying mechanism is still unknown,which is unfavorable to guide the design of high performance electrode.Herein,by incorporating layered MnO_(2)with N-doped carbon nanowires,a free-standing cathode with hierarchical core-shell structure(denoted as MnO_(2)@NC)is prepared.Benefiting from the N-doped carbon and rational architecture,the MnO_(2)@NC electrode shows an enhanced specific capacity(325 mAh g^(−1)at 0.1 A g^(−1))and rate performance(90 mAh g^(−1)at 2 A g^(−1)),as well as improved cycling stability.Furthermore,the performance improvement mechanism of MnO_(2)incorporated by N-doped carbon is investigated by X-ray photoelectron spectroscopy(XPS),Raman spectrums and density functional theory(DFT)calculation.The N atom elongates the Mn-O bond and reduces the valence of Mn^(4+)ion in MnO_(2)crystal by delocalizing its electron clouds.Thus,the electrostatic repulsion will be weakened when Zn^(2+)/H^(+)insert into the host MnO_(2)lattices,which is profitable to more cation insertion and faster ion transfer kinetics for higher capacity and rate capability.This work elucidates a fundamental understanding of the functions of N-doped carbon in composite materials and shed light on a practical pathway to optimize other electrode materials.
基金supported by Key Area Research and Development Program of Guangdong Province (2019B110209003)Guangdong Basic and Applied Basic Research Foundation (2019B1515120058,2020A1515011149)+2 种基金National Natural Science Foundation of China (22078374,21776324)National Key R&D Program of China (2018YFD0800703)National Ten Thousand Talent Plan,the Fundamental Research Funds for the Cornell University (19lgzd25)and Hundred Talent Plan (201602)from Sun Yat-sen University.
文摘A robust and green strategy for the selective upgrading of biomass-derived platform chemicals towards highly valuable products is important for the sustainable development.Herein,the efficient electrocatalytic oxidation of biomass-derived furfuryl alcohol(FFA)into furoic acid(FurAc)catalyzed by the electrodeposited non-precious NiFe microflowers was successfully reached under the low temperature and ambient pressure.The 3D hierarchical NiFe microflowers assembled from ultrathin nanosheets were controllably synthesized by the electrodeposition method and uniformly grown on carbon fiber paper(CFP).Electrochemical analysis confirmed that NiFe nanosheets more preferred in the selective oxidation of FFA(FFAOR)than oxygen evolution reaction(OER).The linear sweep voltammetry(LSV)in FFAOR displayed a clear decrease towards lower potential,resulting in 30 mV reduction of overpotential at 20 mA cm^(-2) compared with that of OER.The optimal catalyst Ni_(1)Fe_(2) nanosheets exhibited the highest selectivity of FurAc(94.0%)and 81.4%conversion of FFA within 3 h.Besides,the influence of various reaction parameters on FFAOR was then explored in details.After that,the reaction pathway was investigated and rationally proposed.The outstanding performance for FFAOR can be ascribed to the unique structure of 3D flower-like NiFe nanosheets and oxygen vacancies,resulting in large exposure of active sites,faster electron transfer and enhanced adsorption of reactants.Our findings highlight a facile and convenient mean with a promising green future,which is promising for processing of various biomass-derived platform chemicals into value-added products.
基金funded by the National Key Research and Development Program of China(2017YFA0700103,2018YFA0704502)the National Natural Science Foundation of China(21703248)staffs in BL11B beamline in Shanghai Synchrotron Radiation Facility(SSRF)for their technical assistance(2020-SSRF-PT-012223 and 2021-SSRF-PT-015319)。
文摘The conversion of CO_(2)into value-added chemicals coupled with the storage of intermittent renewable electricity is attractive.CuO nanosheets with an average size and thickness of~30 and~20 nm have been developed,which are in situ reduced into Cu nanosheets during electrochemical CO_(2)reduction reaction(ECO_(2)RR).The derived Cu nanosheets demonstrate much higher selectivity for C2H4production than commercial CuO derived Cu powder,with an optimum Faradaic efficiency of 56.2%and a partial current density of C_(2)H_(4)as large as 171.0 mA cm^(-2)in a gas diffusion flow cell.The operando attenuated total reflectance-Fourier transform infrared spectra measurements and density functional theory simulations illustrate that the high activity and selectivity of Cu nanosheets originate from the edge sites on Cu nanosheets with a coordinate number around 5(4–6),which facilitates the formation of^(*)CHO rather than^(*)COH intermediate,meanwhile boosting the C-C coupling reaction of^(*)CO and^(*)CHO intermediates,which are the critical steps for C_(2)H_(4)formation.
基金the National Natural Science Foundation of China (21776306)。
文摘The introduction of bifunctional groups into low-cost adsorbents for selective adsorption of Ag(I) through synergistic effect will have a profound impact on the recovery of precious metals. Organo silica nanosheets(organo-Si NSs) functionalized by series of azole derivatives(2-mercaptoimidazole(MI), 2-mercaptobenzimidazole(MBT) and 1H-1,2,4-triazole-3-thiol(MTT)), are fabricated and employed for selective removal of Ag(I). The structures of the organo-Si NSs are investigated using several characterization methods. The results of batch adsorption experiments display that the maximum adsorption amounts are 70.3, 103.2 and 139.5 mg·g^(-1) on MI-Si NSs, MBI-Si NSs and MTT-Si NSs for Ag(I) ions, and reach rapid equilibrium within 10–30 min. The adsorption processes are chemisorption and fit pseudo-second-order kinetic model and Langmuir adsorption isotherm model. Notably, MTT-Si NSs is greatly selective for Ag(I) in multicomponent system, and the distribution coefficient value of Ag(I) ions reaches 2331.26 ml·g^(-1). The reusability of organo-Si NSs is verified by four cycles of regeneration tests with 0.1 mol·L^(-1) HNO_(3) as the eluent. A combination of experimental, structural along with theoretical analysis is conducted to proclaim the structure-adsorptivity relationship:(i) The adsorption mechanisms are attributed to complexation.(ii) The amino group and sulfhydryl group of MTT-Si NSs as well as MBISi NSs may have synergistic impacts on Ag(I) capture.(iii) The differences in adsorption behavior and selectivity of the three organo-Si NSs are mainly related to the form of function groups, charge density and steric hindrance of adsorbent. This work not only sheds light on the promise of functionalized organo-Si NSs for the rapid and selective removal/enrichment of Ag(I) ions in complex water systems,but also provides new insights for designing cost-effective Si NSs-based adsorbents.
基金supported by the National Natural Science Foundation of China(52074320)Petrochina Strategic Cooperation Science and Technology Project(ZLZX2020-01-04-03)。
文摘Janus amphiphilic polymer nanosheets(JAPNs)with anisotropic morphology and distinctive perfor-mance have aroused widespread interest.However,due to the difficulty in synthesis and poor dispersion stability,JAPNs have been scarcely reported in the field of enhancing oil recovery(EOR).Herein,a kind of organic-based flexible JAPNs was prepared by paraffin emulsion methods.The lateral sizes of JAPNs were ranging from hundreds of nanometers to several micrometers and the thickness was about 3 nm.The organic-based nanosheets were equipped with remarkably flexible structures,which could improve their injection performance.The dispersion and interfacial properties of JAPNs were studied systematically.By modification of crosslinking agent containing multiple amino groups,the JAPNs had excellent hydro-philicity and salt resistance compared with conventional inorganic or composite nanosheets.The settling time of nanosuspension with NaCl and CaCl_(2) at a low salinity of 1000 mg/L was over 240 h.The value could also remain 124 h under the salinity of 10,000 mg/L NaCl.With the dual functionalities of Janus amphiphilic nature and nanoparticles'Pickering effect,JAPNs could change rock wettability and form emulsions as"colloidal surfactants",In particular,a new technology called optical microrheology was pioneered to explore the destabilization state of nanosuspensions for the first time.Since precipitation lagged behind aggregation,especially for stable suspension systems,the onset of the unstable behavior was difficult to be detected by conventional methods,which should be the indicator of reduced effec-tiveness for nanofluid products.In addition,the oil displacement experiments demonstrated that the JAPNs could enhance oil recovery by 17.14%under an ultra-low concentration of 0.005%and were more suitable for low permeability cores.The findings can help for a better understanding of the material preparation of polymer nanosheets.We also hope that this study could shed more light on the nano-flooding technology for EOR.
