Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology r...Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.展开更多
Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticle...Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.展开更多
With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption...With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.展开更多
Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently req...Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently required.Herein,utilizing the low boiling point of Zn,porous N-doped carbon was fabricated by carbonization of ZIF-8(Zn)at different temperature,and the microwave absorption performance was investigated.The porous N-doped carbon inherits the high porosity of ZIF-8 precursor.By increasing the carbonization temperature,the contents of Zn and N elements are decreased;the graphitization degree is improved;however,the specific surface area and porosity are increased first and then decreased.When the carbonization temperature is 1000°C,the porous N-doped carbon behaves enhanced microwave absorption.With an ultrathin thickness of 1.29 mm,the ideal RL reaches-50.57 dB at 16.95 GHz and the effective absorption bandwidth is 4.17 GHz.The mechanism of boosted microwave absorption is ascribed to the competition of graphitization and porosity as well as N dopants,resulting in high dielectric loss capacity and good impedance matching.The porous structure can prolong the pathways and raise the contact opportunity between microwaves and porous carbon,causing multiple scattering,interface polarization,and improved impedance matching.Besides,the N dopants can induce electron polarization and defect polarization.These results give a new insight to construct lightweight carbon-based microwave absorbents by regulating the graphitization and porosity.展开更多
N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial ...N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial Coulombic efficiency(ICE).In this study,high N-doped and low graphitic-N carbons(LGNCs)with enhanced ICE were synthesized by taking advantage of a denitrification strategy for graphitic carbon nitride(g-C_(3)N_(4)).In brief,more than 14.5 at%of N from g-C_(3)N_(4)(55.1 at%N)was retained by reacting graphitic-N with lithium,which was subsequently removed.As graphitic-N is largely responsible for the irreversible capacity,the anode's performance was significantly increased.Compared to general N-doped carbons with high graphitic-N proportion(>50%)and low N content(<15 at%),LGNCs delivered a low proportion of 10.8%-17.2% within the high N-doping content of 14.5-42.7 at%,leading to an enhanced specific capacity of 1499.9mAh g^(-1) at an ICE of 93.7% for the optimal sample of LGNC(4:1).This study provides a facile strategy to control the N content and speciation,achieving both high Li+storage capacity and high ICE,and thus promoting research and application of N-doped carbon materials.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocataly...Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocatalysts, but it remains one challenge to finely engineer the active sites and porosity. Herein, we demonstrated that ionic porous polyamides were a kind of versatile precursors to prepare functional carbon materials in a one-step pyrolysis process. The polyamide precursors allowed the maintenance of abundant N species at high temperatures. The existence of ionic moieties and large specific surface area of the precursors promoted the formation of larger porosity carbon with a large specific surface area and sufficient active graphitic-N species by controlling the pyrolysis temperature. The catalyst was highly selective in the CO_(2) RR to produce CO with a maximum Faraday efficiency above 99%, attributable to the improved mass transfer in a large porosity system. This work shows that ionic polyamides are promising carbon precursors for the fabrication of metal-free electrocatalysts for CO_(2) RR.展开更多
Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient...Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.展开更多
Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water...Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.展开更多
Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated str...Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated strategy to anchor Co species on N-doped carbon nanorods for efficient ORR.Featuring ultrahigh N-doping(10.29 at.%),monodisperse Co nanocrystal decoration,and well-dispersed Co-N_(x)functionalization,the obtained Co-decorated N-doped carbon nanorods(Co@NCNR)exhibit a decent ORR performance comparable to commercial Pt/C in alkaline media.Aqueous ZABs have been assembled using Co@NCNR as the cathode catalyst.The assembled ZABs manifest high initial open-circuit voltage as well as high energy density.In addition,the Co@NCNR also demonstrates ideal ORR performance in quasi-solid-state ZABs.展开更多
An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and ...An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and stirring at 70°C for 14 h.The morphology and structure of the rGO-like carbon were investigated by electron microscopies and Raman spectroscopy.The presence of C-N functional groups was analyzed by Fourier transform infrared and synchrotron X-ray photoemission spectroscopy,while the particle and the specific capacitance were measured by particle sizer and cyclic voltammetry.The highest specific capacitance of 72.78 F/g is achieved by the sample with 20%urea,having the smallest particles size and the largest surface area.The corresponding sample has shown to be constituted by the appropriate amount of C–N pyrrolic and pyridinic defects.展开更多
Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings th...Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.展开更多
Reconstituted wood panels have several advantages in terms of ease of manufacturing,but their shorter life span results in a huge amount of reconstituted wood panels being discarded in sorting centers yearly.Currently...Reconstituted wood panels have several advantages in terms of ease of manufacturing,but their shorter life span results in a huge amount of reconstituted wood panels being discarded in sorting centers yearly.Currently,the most common approach for dealing with this waste is incineration.In this study,reconstituted wood panels were converted into activated biochar through a two-step thermochemical process:(i)biochar production using pilot scale fast pyrolysis at 250 kg/h and 450℃;and(ii)a physical activation at three temperatures(750℃,850℃ and 950℃)using an in-house activation furnace(1 kg/h).Results showed that the first stage removed about 66% of the nitrogen from the wood panels in the form of NO,NH3,and trimethylamine,which were detected in small amounts compared to emitted CO_(2).Compared to other types of thermochemical conversion methods(e.g.,slow pyrolysis),isocyanic acid and hydrogen cyanide were not detected in this study.The second stage produced activated biochar with a specific surface area of up to 865 m^(2)/g at 950℃.The volatile gases generated during activation were predominantly composed of toluene and benzene.This two-step process resulted in nitrogen-rich carbon in the form of pyrrolic and pyridinic nitrogen.Activated biochars were then evaluated for their SO_(2) retention performance and showed an excellent adsorption capacity of up to 2140 mg/g compared to 65 mg/g for a commercial activated carbon(889 m^(2)/g).End-of-life reconstituted wood panels and SO_(2) gas are problematic issues in Canada where the economy largely revolves around forestry and mining industries.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
Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability...Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability and operation speed is one of key factors to restrain the development of phase-change memory.Here,N-doped Ge_(2)Sb_(2)Te_(5)-based optoelectronic hybrid memory is proposed to simultaneously implement high thermal stability and ultrafast operation speed.The picosecond laser is adopted to write/erase information based on reversible phase transition characteristics whereas the resistance is detected to perform information readout.Results show that when N content is 27.4 at.%,N-doped Ge_(2)Sb_(2)Te_(5)film possesses high ten-year data retention temperature of 175℃and low resistance drift coefficient of 0.00024 at 85℃,0.00170 at 120℃,and 0.00249 at 150℃,respectively,owing to the formation of Ge–N,Sb–N,and Te–N bonds.The SET/RESET operation speeds of the film reach 520 ps/13 ps.In parallel,the reversible switching cycle of the corresponding device is realized with the resistance ratio of three orders of magnitude.Four-level reversible resistance states induced by various crystallization degrees are also obtained together with low resistance drift coefficients.Therefore,the N-doped Ge_(2)Sb_(2)Te_(5)thin film is a promising phase-change material for ultrafast multilevel optoelectronic hybrid storage.展开更多
Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which ot...Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.展开更多
The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In t...The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.展开更多
Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical...Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical conductivity.To mitigate these issues,free-standing N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites(Si/C-ZIF-8/CNFs)are designed and synthesized by electrospinning and carbonization methods,which present greatly enhanced electrochemical properties for lithium-ion battery anodes.This particular structure alleviates the volume variation,promotes the formation of stable solid electrolyte interphase(SEI)film,and improves the electrical conductivity.As a result,the as-obtained free-standing Si/C-ZIF-8/CNFs electrode delivers a high reversible capacity of 945.5 mAh g^(-1) at 0.2 A g^(-1) with a capacity retention of 64% for 150 cycles,and exhibits a reversible capacity of 538.6 mA h g^(-1) at 0.5 A g^(-1) over 500 cycles.Moreover,the full cell composed of a freestanding Si/C-ZIF-8/CNFs anode and commercial LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM)cathode shows a capacity of 63.4 mA h g^(-1) after 100 cycles at 0.2 C,which corresponds to a capacity retention of 60%.This rational design could provide a new path for the development of high-performance Si-based anodes.展开更多
Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their ou...Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their outstanding electrical conductivity, hierarchical porous structure, intrinsic heteroatom doping, and environmental friendliness. Here, we investigate the potential of hierarchical N-doped porous carbon (NPC) derived from jackfruit rags through a facile pyrolysis as an anode material for SIBs. The cycling performance of NPC at 1 A/g for 2000 cycles featured a stable reversible capacity of 122.3 mA h/g with an outstanding capacity retention of 99.1%. These excellent electrochemical properties can be attributed to the unique structure of NPC;it features hierarchical porosity with abundant carbon edge defects and large speci c surface areas. These results illuminate the potential application of jackfruit rags-derived porous carbon in SIBs.展开更多
NaTaO_(3-x)N_x catalysts were synthesized by a hydrothermal(H) and a solid-state(S) methods in this study.The H-and S-NaTaO_(3-x)N_x samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(S...NaTaO_(3-x)N_x catalysts were synthesized by a hydrothermal(H) and a solid-state(S) methods in this study.The H-and S-NaTaO_(3-x)N_x samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV–visible(UV–vis) diffuse reflectance spectroscopy, and photoluminescence(PL) spectroscopy. The XRD patterns of the H-and S-samples showed peaks indexed to the pure phase of perovskite NaTaO_3 and minor peaks assignable to Ta_3N_5 at various synthesis temperatures. Substitution of oxygen by nitrogen ions causes the light absorption of the H-and S-NaTaO_(3-x)N_x samples to be extended to the 600–650 nm region, thus making the samples visible-light active. The NaTaO_(3-x)N_x samples exhibited photocatalytic activity for H_2 and O_2 evolution from aqueous methanol and silver nitrate solutions under visible-light irradiation. The UV–vis and PL spectra of the Hand S-catalysts revealed the presence of cationic vacancies and reduced metallic species, which acted as recombination centers. These results demonstrated that the preparation method plays a critical role in the formation of defect states, thereby governing the photocatalytic activity of the NaTaO_(3-x)N_x catalysts.展开更多
Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated g...Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212,52102058,52204414,52204413,and 52204412)the National Key R&D Program of China (Nos.2021YFC1910504,2019YFC1907101,2019YFC1907103,and 2017YFB0702304)+7 种基金the Key R&D Program of Ningxia Hui Autonomous Region,China (Nos.2021BEG01003 and2020BCE01001)the Xijiang Innovation and Entrepreneurship Team,China (No.2017A0109004)the Macao Young Scholars Program (No.AM2022024),Chinathe Beijing Natural Science Foundation (Nos.L212020 and 2214073),Chinathe Guangdong Basic and Applied Basic Research Foundation,China (Nos.2021A1515110998 and 2020A1515110408)the China Postdoctoral Science Foundation (No.2022M710349)the Fundamental Research Funds for the Central Universities,China (Nos.FRF-BD-20-24A,FRF-TP-20-031A1,FRF-IC-19-017Z,and 06500141)the Integration of Green Key Process Systems MIIT and Scientific and Technological Innovation Foundation of Foshan,China(Nos.BK22BE001 and BK21BE002)。
文摘Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.
基金support by the National Natural Science Foundation of China(U21A20306,U20A20152)Natural Science Foundation of Hebei Province(B2022202077).
文摘Enhancing the stability of supported noble metal catalysts emerges is a major challenge in both science and industry.Herein,a heterogeneous Pd catalyst(Pd/NCF)was prepared by supporting Pd ultrafine metal nanoparticles(NPs)on nitrogen-doped carbon;synthesized by using F127 as a stabilizer,as well as chitosan as a carbon and nitrogen source.The Pd/NCF catalyst was efficient and recyclable for oxidative carbonylation of phenol to diphenyl carbonate,exhibiting higher stability than Pd/NC prepared without F127 addition.The hydrogen bond between chitosan(CTS)and F127 was enhanced by F127,which anchored the N in the free amino group,increasing the N content of the carbon material and ensuring that the support could provide sufficient N sites for the deposition of Pd NPs.This process helped to improve metal dispersion.The increased metal-support interaction,which limits the leaching and coarsening of Pd NPs,improves the stability of the Pd/NCF catalyst.Furthermore,density functional theory calculations indicated that pyridine N stabilized the Pd^(2+)species,significantly inhibiting the loss of Pd^(2+)in Pd/NCF during the reaction process.This work provides a promising avenue towards enhancing the stability of nitrogen-doped carbon-supported metal catalysts.
基金support from the Natural Science Foundation of Jilin Province(Grant No.20200201073JC)the National Natural Science Foundation of China(Grant No.52130101)+1 种基金Interdisciplinary Integration and Innovation Project of JLU(Grant No.JLUXKJC2021ZY01)the Fundamental Research Funds for the Central Universities.
文摘With the advantage of fast charge transfer,heterojunction engineering is identified as a viable method to reinforce the anodes'sodium storage performance.Also,vacancies can effectively strengthen the Na+adsorption ability and provide extra active sites for Na+adsorption.However,their synchronous engineering is rarely reported.Herein,a hybrid of Co_(0.85)Se/WSe_(2) heterostructure with Se vacancies and N-doped carbon polyhedron(CoWSe/NCP)has been fabricated for the first time via a hydrothermal and subsequent selenization strategy.Spherical aberration-corrected transmission electron microscopy confirms the phase interface of the Co_(0.85)Se/WSe_(2) heterostructure and the existence of Se vacancies.Density functional theory simulations reveal the accelerated charge transfer and enhanced Na+adsorption ability,which are contributed by the Co_(0.85)Se/WSe_(2) heterostructure and Se vacancies,respectively.As expected,the CoWSe/NCP anode in sodium-ion battery achieves outstanding rate capability(339.6 mAh g^(−1) at 20 A g^(−1)),outperforming almost all Co/W-based selenides.
基金financially supported by National Natural Science Foundation of China(Nos.51572218 and 11504293)Natural Science Foundation of Shaanxi Province(No.2019JM-138)+1 种基金Natural Science Foundation from Department of Science and Technology of Shaanxi Province(Nos.2021JQ-431,2021JM-304,and 2021JQ-427)Scientific Research Program Funded by Shaanxi Provincial Education Department(No.20JK0946)。
文摘Porous carbon-based materials are promised to be lightweight dielectric microwave absorbents.Deeply understanding the influence of graphitization grade and porous structure on the dielectric parameters is urgently required.Herein,utilizing the low boiling point of Zn,porous N-doped carbon was fabricated by carbonization of ZIF-8(Zn)at different temperature,and the microwave absorption performance was investigated.The porous N-doped carbon inherits the high porosity of ZIF-8 precursor.By increasing the carbonization temperature,the contents of Zn and N elements are decreased;the graphitization degree is improved;however,the specific surface area and porosity are increased first and then decreased.When the carbonization temperature is 1000°C,the porous N-doped carbon behaves enhanced microwave absorption.With an ultrathin thickness of 1.29 mm,the ideal RL reaches-50.57 dB at 16.95 GHz and the effective absorption bandwidth is 4.17 GHz.The mechanism of boosted microwave absorption is ascribed to the competition of graphitization and porosity as well as N dopants,resulting in high dielectric loss capacity and good impedance matching.The porous structure can prolong the pathways and raise the contact opportunity between microwaves and porous carbon,causing multiple scattering,interface polarization,and improved impedance matching.Besides,the N dopants can induce electron polarization and defect polarization.These results give a new insight to construct lightweight carbon-based microwave absorbents by regulating the graphitization and porosity.
基金National Natural Science Foundation of China,Grant/Award Number:51777138Deutsche Forschungsgemeinschaft(DFG,German Research Foundation),Grant/Award Number:491183248Open Access Publishing Fund of the University of Bayreuth。
文摘N-doped carbons as one of the most prominent anode materials to replace standard graphite exhibit outstanding Li+storage performance.However,N-doped carbon anodes still suffer from low N-doping levels and low initial Coulombic efficiency(ICE).In this study,high N-doped and low graphitic-N carbons(LGNCs)with enhanced ICE were synthesized by taking advantage of a denitrification strategy for graphitic carbon nitride(g-C_(3)N_(4)).In brief,more than 14.5 at%of N from g-C_(3)N_(4)(55.1 at%N)was retained by reacting graphitic-N with lithium,which was subsequently removed.As graphitic-N is largely responsible for the irreversible capacity,the anode's performance was significantly increased.Compared to general N-doped carbons with high graphitic-N proportion(>50%)and low N content(<15 at%),LGNCs delivered a low proportion of 10.8%-17.2% within the high N-doping content of 14.5-42.7 at%,leading to an enhanced specific capacity of 1499.9mAh g^(-1) at an ICE of 93.7% for the optimal sample of LGNC(4:1).This study provides a facile strategy to control the N content and speciation,achieving both high Li+storage capacity and high ICE,and thus promoting research and application of N-doped carbon materials.
基金support from the National Natural Science Foundation of China ( 22072065, 22178162, U1662107, and 21476109)Six talent peaks project in Jiangsu Province (JNHB-035)+1 种基金State Key Laboratory of Materials-Oriented Chemical Engineering (KL18-09)the Project of Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)。
文摘Electrochemical CO_(2) reduction reaction(CO_(2) RR) has attracted growing attention in energy storage and sustainable production of fuels and chemicals. N-doped carbon materials are preferred metal-free electrocatalysts, but it remains one challenge to finely engineer the active sites and porosity. Herein, we demonstrated that ionic porous polyamides were a kind of versatile precursors to prepare functional carbon materials in a one-step pyrolysis process. The polyamide precursors allowed the maintenance of abundant N species at high temperatures. The existence of ionic moieties and large specific surface area of the precursors promoted the formation of larger porosity carbon with a large specific surface area and sufficient active graphitic-N species by controlling the pyrolysis temperature. The catalyst was highly selective in the CO_(2) RR to produce CO with a maximum Faraday efficiency above 99%, attributable to the improved mass transfer in a large porosity system. This work shows that ionic polyamides are promising carbon precursors for the fabrication of metal-free electrocatalysts for CO_(2) RR.
基金supported by the National Science Foundation of China(21805235)the Opening Foundation of Creative Platform of the Key Laboratory of the Education Department of Hunan Province(20K131)the Construct Program of the Key Discipline in Hunan Province。
文摘Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.
基金the National Natural Science Foundation of China(Nos.52072151,52171211,52102253,52271218,U22A20145)the Jinan Independent Innovative Team(2020GXRC015)+1 种基金the Major Program of Shandong Province Natural Science Foundation(ZR2021ZD05)the Science and Technology Program of University of Jinan(XKY2119).
文摘Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.
基金supported by the National Natural Science Foundation of China(52072283)the National Key Research and Development Program of China(2020YFA0715000)+1 种基金Shenzhen Fundamental Research Program(JCYJ20190809114409397)supported by the Fundamental Research Funds for the Central Universities(WUT:2021III016GX).
文摘Developing efficient oxygen reduction reaction(ORR)catalyst is essential for the practical application of Zn-air batteries(ZABs).In this contribution,we develop a novel zeolitic imidazolate framework(ZIF)-mediated strategy to anchor Co species on N-doped carbon nanorods for efficient ORR.Featuring ultrahigh N-doping(10.29 at.%),monodisperse Co nanocrystal decoration,and well-dispersed Co-N_(x)functionalization,the obtained Co-decorated N-doped carbon nanorods(Co@NCNR)exhibit a decent ORR performance comparable to commercial Pt/C in alkaline media.Aqueous ZABs have been assembled using Co@NCNR as the cathode catalyst.The assembled ZABs manifest high initial open-circuit voltage as well as high energy density.In addition,the Co@NCNR also demonstrates ideal ORR performance in quasi-solid-state ZABs.
基金supported by“Hibah Penelitian Dasar Kompetitif Nasional”,Ministry of Education,Culture,Research and Technology,Indonesia,2021–2022(D).The use of the synchrotron XPES facility at SLRI(Public Organization),Thailand,and some experimental facilities at UNIMAP and UPM,Malaysia,would also be appreciated.
文摘An rGO−like carbon compound has been synthesized from biomass,i.e.,old coconut shell,by a carbonization process followed by heating at 400°C for 5 h.The nitrogen doping was achieved by adding the urea(CH4N2O)and stirring at 70°C for 14 h.The morphology and structure of the rGO-like carbon were investigated by electron microscopies and Raman spectroscopy.The presence of C-N functional groups was analyzed by Fourier transform infrared and synchrotron X-ray photoemission spectroscopy,while the particle and the specific capacitance were measured by particle sizer and cyclic voltammetry.The highest specific capacitance of 72.78 F/g is achieved by the sample with 20%urea,having the smallest particles size and the largest surface area.The corresponding sample has shown to be constituted by the appropriate amount of C–N pyrrolic and pyridinic defects.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51803151,51973152,51773147,52173078,52130303,51973158)the State Key Program of National Natural Science Foundation of China(No.51633007)the Seed Foundation of Tianjin University(No.2105018).
文摘Optimizing the structure of electrode materials is one of the most effective strategies for designing high-power microbial fuel cells(MFCs).However,electrode materials currently suffer from a series of shortcomings that limit the output of MFCs,such as high intrinsic resistance,poor electrolyte wettability,and low microbial load capacity.Here,a three-dimensional(3D)nitrogen-doped multiwalled carbon nanotube/graphene(N-MWCNT/GA)composite aerogel is synthesized as the anode for MFCs.Comparing nitrogen-doped GA,MWCNT/GA,and N-MWCNT/GA,the macroporous hydrophilic N-MWCNT/GA electrode with an average pore size of 4.24μm enables high-density loading of the microbes and facilitates extracellular electron transfer with low intrinsic resistance.Consequently,the hydrophilic surface of N-MWCNT can generate high charge mobility,enabling a high-power output performance of the MFC.In consequence,the MFC system based on N-MWCNT/GA anode exhibits a peak power density and output voltage of 2977.8 mW m^(−2)and 0.654 V,which are 1.83 times and 16.3%higher than those obtained with MWCNT/GA,respectively.These results demonstrate that 3D N-MWCNT/GA anodes can be developed for high-power MFCs in different environments by optimizing their chemical and microstructures.
基金funded by the Ministere de l’Economie,de la Science et de l’Innovation du Quebec,the Natural Sciences and Engineering Research Council of Canada(NSERC)the Consortium de recherche et innovations en bioprocedes industriels au Quebec(Cribiq)+1 种基金the Canada Research Chair Program,the College of Abitibi-Temiscaminguethe Industrial Waste Technology Centre(Centre Technologique des Residus Industriels)through its partner on this project,Airex Energy.
文摘Reconstituted wood panels have several advantages in terms of ease of manufacturing,but their shorter life span results in a huge amount of reconstituted wood panels being discarded in sorting centers yearly.Currently,the most common approach for dealing with this waste is incineration.In this study,reconstituted wood panels were converted into activated biochar through a two-step thermochemical process:(i)biochar production using pilot scale fast pyrolysis at 250 kg/h and 450℃;and(ii)a physical activation at three temperatures(750℃,850℃ and 950℃)using an in-house activation furnace(1 kg/h).Results showed that the first stage removed about 66% of the nitrogen from the wood panels in the form of NO,NH3,and trimethylamine,which were detected in small amounts compared to emitted CO_(2).Compared to other types of thermochemical conversion methods(e.g.,slow pyrolysis),isocyanic acid and hydrogen cyanide were not detected in this study.The second stage produced activated biochar with a specific surface area of up to 865 m^(2)/g at 950℃.The volatile gases generated during activation were predominantly composed of toluene and benzene.This two-step process resulted in nitrogen-rich carbon in the form of pyrrolic and pyridinic nitrogen.Activated biochars were then evaluated for their SO_(2) retention performance and showed an excellent adsorption capacity of up to 2140 mg/g compared to 65 mg/g for a commercial activated carbon(889 m^(2)/g).End-of-life reconstituted wood panels and SO_(2) gas are problematic issues in Canada where the economy largely revolves around forestry and mining industries.
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Project supported by the National Natural Science Foundation of China(Grant Nos.62205231 and 22002102)the Postgraduate Research&Practice Innovation Program of Jiangsu Province,China(Grant No.KYCX223271)Jiangsu Key Laboratory for Environment Functional Materials。
文摘Multilevel phase-change memory is an attractive technology to increase storage capacity and density owing to its high-speed,scalable and non-volatile characteristics.However,the contradiction between thermal stability and operation speed is one of key factors to restrain the development of phase-change memory.Here,N-doped Ge_(2)Sb_(2)Te_(5)-based optoelectronic hybrid memory is proposed to simultaneously implement high thermal stability and ultrafast operation speed.The picosecond laser is adopted to write/erase information based on reversible phase transition characteristics whereas the resistance is detected to perform information readout.Results show that when N content is 27.4 at.%,N-doped Ge_(2)Sb_(2)Te_(5)film possesses high ten-year data retention temperature of 175℃and low resistance drift coefficient of 0.00024 at 85℃,0.00170 at 120℃,and 0.00249 at 150℃,respectively,owing to the formation of Ge–N,Sb–N,and Te–N bonds.The SET/RESET operation speeds of the film reach 520 ps/13 ps.In parallel,the reversible switching cycle of the corresponding device is realized with the resistance ratio of three orders of magnitude.Four-level reversible resistance states induced by various crystallization degrees are also obtained together with low resistance drift coefficients.Therefore,the N-doped Ge_(2)Sb_(2)Te_(5)thin film is a promising phase-change material for ultrafast multilevel optoelectronic hybrid storage.
基金supported by the National Natural Science Foundation of China (51702225)the National Key Research and Development Program (2016YFA0200103)+2 种基金the Natural Science Foundation of Jiangsu Province (BK20170336)the support from Suzhou Key Laboratory for Advanced Carbon MaterialsWearable Energy Technologies, Suzhou, China。
文摘Developing high-performance anodes for potassium ion batteries(KIBs) is of paramount significance but remains challenging.In the normal sense,electrode materials are prepared by ubiquitous wet chemical routes,which otherwise might not be versatile enough to create desired heterostructures and/or form clean interfacial areas for fast transport of K-ions and electrons.Along this line,rate capability/cycling stability of resulting KIBs are greatly handicapped.Herein we present an all-chemical vapor deposition approach to harness the direct synthesis of nitrogen-doped graphene(NG)/rhenium diselenide(ReSe_2)hybrids over three-dimensional MXene supports as superior heterostructure anode material for KIBs.In such an innovative design,1 T'-ReSe2 nanoparticles are sandwiched in between the NG coatings and MXene frameworks via strong interfacial interactions,thereby affording facile K~+ diffusion,enhancing overall conductivity,boosting high-power performance and reinforcing structural stability of electrodes.Thus-constructed anode delivers an excellent rate performance of 138 mAh g^(-1) at 10.0 A g^(-1) and a high reversible capacity of 90 mAh g^(-1) at 5 A g^(-1) after 300 cycles.Furthermore,the potassium storage mechanism has been systematically probed by advanced in situlex situ characterization techniques in combination with first principles computations.
基金supported by the National Natural Science Foundation of China(21421001,21573115,21875118)Tianjin Science and Technology Commission(18JCTPJC55900)+1 种基金the Natural Science Foundation of Tianjin(17JCYBJC17100,19JCZDJC37700)the 111 Project(B12015).
文摘The design and development of low-cost,efficient,and stable bifunctional electrocatalysts for the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are desirable for rechargeable metal-air batteries.In this work,N-doped porous hollow carbon spheres encapsulated with ultrafine Fe/Fe3O4 nanoparticles(FeOx@N-PHCS)were fabricated by impregnation and subsequent pyrolysis,using melamine-formaldehyde resin spheres as self-sacrifice templates and polydopamine as N and C sources.The sufficient adsorption of Fe3+on the polydopamine endowed the formation of Fe-Nx species upon high-temperature carbonization.The prepared FeOx@N-PHCS has advanced features of large specific surface area,porous hollow structure,high content of N dopants,sufficient Fe-Nx species and ultrafine FeOx nanoparticles.These features endow FeOx@N-PHCS with enhanced mass transfer and considerable active sites,leading to high activity and stability in catalyzing ORR and OER in alkaline electrolyte.Furthermore,the rechargeable Zn-air battery with FeOx@N-PHCS as air cathode catalyst exhibits a large peak power density,narrow charge-discharge potential gap and robust cycling stability,demonstrating the potential of the fabricated FeOx@N-PHCS as a promising electrode material for metal-air batteries.This new finding may open an avenue for rational design of bifunctional catalysts by integrating different active components within all-in-one catalyst for different electrochemical reactions.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.21965034,21703185,U1903217,51901013,and 21666037)the Xinjiang Autonomous Region Major Projects(2017A02004)+4 种基金the Leading Project Foundation of Science Department of Fujian Province(Grant No.2018H0034)the Resource Sharing Platform Construction Project of Xinjiang Province(PT1909)the Nature Science Foundation of Xinjiang Province(2017D01C074)the Opening Project of National Joint Engineering Research Center for Abrasion Control and Molding of Metal Materials,Henan University of Science and Technology(No.HKDNM201906)the Young Scholar Science Foundation of Xinjiang Educational Institutions(XJEDU2016S030)。
文摘Dramatic capacity fading and poor rate performance are two main obstacles that severely hamper the widespread application of the Si anode owing to its large volume variation during cycling and low intrinsic electrical conductivity.To mitigate these issues,free-standing N-doped porous carbon nanofibers sheathed pumpkin-like Si/C composites(Si/C-ZIF-8/CNFs)are designed and synthesized by electrospinning and carbonization methods,which present greatly enhanced electrochemical properties for lithium-ion battery anodes.This particular structure alleviates the volume variation,promotes the formation of stable solid electrolyte interphase(SEI)film,and improves the electrical conductivity.As a result,the as-obtained free-standing Si/C-ZIF-8/CNFs electrode delivers a high reversible capacity of 945.5 mAh g^(-1) at 0.2 A g^(-1) with a capacity retention of 64% for 150 cycles,and exhibits a reversible capacity of 538.6 mA h g^(-1) at 0.5 A g^(-1) over 500 cycles.Moreover,the full cell composed of a freestanding Si/C-ZIF-8/CNFs anode and commercial LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)(NCM)cathode shows a capacity of 63.4 mA h g^(-1) after 100 cycles at 0.2 C,which corresponds to a capacity retention of 60%.This rational design could provide a new path for the development of high-performance Si-based anodes.
基金financially supported by National Natural Science Foundation of China (Nos. 21875253, 21703249)the 1000 Plan Professorship for Young Talents
文摘Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their outstanding electrical conductivity, hierarchical porous structure, intrinsic heteroatom doping, and environmental friendliness. Here, we investigate the potential of hierarchical N-doped porous carbon (NPC) derived from jackfruit rags through a facile pyrolysis as an anode material for SIBs. The cycling performance of NPC at 1 A/g for 2000 cycles featured a stable reversible capacity of 122.3 mA h/g with an outstanding capacity retention of 99.1%. These excellent electrochemical properties can be attributed to the unique structure of NPC;it features hierarchical porosity with abundant carbon edge defects and large speci c surface areas. These results illuminate the potential application of jackfruit rags-derived porous carbon in SIBs.
基金the financial support from the Ministry of Science and Technology,Taiwan(MOST 104-2218-E-033-006-MY2)
文摘NaTaO_(3-x)N_x catalysts were synthesized by a hydrothermal(H) and a solid-state(S) methods in this study.The H-and S-NaTaO_(3-x)N_x samples were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), UV–visible(UV–vis) diffuse reflectance spectroscopy, and photoluminescence(PL) spectroscopy. The XRD patterns of the H-and S-samples showed peaks indexed to the pure phase of perovskite NaTaO_3 and minor peaks assignable to Ta_3N_5 at various synthesis temperatures. Substitution of oxygen by nitrogen ions causes the light absorption of the H-and S-NaTaO_(3-x)N_x samples to be extended to the 600–650 nm region, thus making the samples visible-light active. The NaTaO_(3-x)N_x samples exhibited photocatalytic activity for H_2 and O_2 evolution from aqueous methanol and silver nitrate solutions under visible-light irradiation. The UV–vis and PL spectra of the Hand S-catalysts revealed the presence of cationic vacancies and reduced metallic species, which acted as recombination centers. These results demonstrated that the preparation method plays a critical role in the formation of defect states, thereby governing the photocatalytic activity of the NaTaO_(3-x)N_x catalysts.
基金Y.Hou expresses appreciation of the assistance of the NSFC 51702284 and 21878270Zhejiang Provincial Natural Science Foundation of China(LR19B060002)the Startup Foundation for Hundred-Talent Program of Zhejiang University(112100-193820101/001/022).
文摘Demand of highly efficient earth-abundant transition metal-based electrocatalysts to replace noble metal materials for boosting oxygen evolution reaction(OER)is rapidly growing.Herein,an electrochemically exfoliated graphite(EG)foil supported bimetallic selenide encased in N-doped carbon(EG/(Co,Ni)Se2-NC)hybrid is developed and synthesized by a vapor-phase hydrothermal strategy and subsequent selenization process.The as-prepared EG/(Co,Ni)Se2-NC hybrid exhibits a core-shell structure where the particle diameter of(Co,Ni)Se2 core is about 70 nm and the thickness of N-doped carbon shell is approximately 5 nm.Benefitting from the synergistic effects between the combination of highly active Co species and improved electron transfer from Ni species,and N-doped carbon,the EG/(Co,Ni)Se2-NC hybrid shows remarkable electrocatalytic activity toward OER with a comparatively low overpotential of 258 mV at an current density of 10 mA cm?2 and a small Tafel slope of 73.3 mV dec?1.The excellent OER catalysis performance of EG/(Co,Ni)Se2-NC hybrid is much better than that of commercial Ir/C(343 mV at 10 mA cm?2 and 98.1 mV dec?1),and even almost the best among all previously reported binary CoNi selenide-based OER electrocatalysts.Furthermore,in situ electrochemical Raman spectroscopy combined with ex situ X-ray photoelectron spectroscopy analysis indicates that the superb OER catalysis activity can be attributed to the highly active Co-OOH species and modified electron transfer process from Ni element.
