Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using model...Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.展开更多
Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidatio...Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.展开更多
With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative...With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).展开更多
Searching new structured black phosphorus(BP)and exploring intriguing functions and applications have become a hot topic so far.Here,we introduce a novel Iso-type black phosphorus heterostructure guided by first princ...Searching new structured black phosphorus(BP)and exploring intriguing functions and applications have become a hot topic so far.Here,we introduce a novel Iso-type black phosphorus heterostructure guided by first principle calculation,which features unique heterointerface and electronic coupling interaction via stacking assembly of exfoliated black phosphorus(EBP)and amine-functionalized EBP(N-EBP).Inspired by the theoretical results,we constructed the Iso-type heterostructure comprising of ultrathin exfoliated few-layered EBP and N-EBP,both of which were derived from identical bulk BP.The purposive amine-functionalization not only creates positively-charged P atoms on N-EBP as effective active sites via N-induced intramolecular electron transfer(IET)but also endows N-EBP with lower work function relative to EBP,while the unique EBP/N-EBP Iso-type heterostructure engenders directional heterointerfacial electron transfer(HET).The coupled IET/HET effects optimize the charge redistribution to afford favorable O_(2)adsorption.In this case,our unique strategy for the first time exploits the inherent catalytic capability of BP toward the oxygen reduction reaction(ORR)and enables the first use of BP as metal-free ORR catalysts for Zn-air cells.The newly-designed heterostructure facilitates a 4-e^(-)transfer ORR relative to inactive EBP or N-EBP.Importantly,the polymer-shielded heterostructure acts as efficient air electrodes to endow a primary Zn-air cell with high stability,large capacity and high energy density—superior to the commercial Pt/C-enabled cell.This study as the first report on metal-free BP-based ORR catalysts and air electrodes not only extends BP's application scopes but also renders new insight toward design of electronically-coupled superstructures for energy-related applications.展开更多
To improve anaerobic digestion(AD)efficiency of rice straw,solid alkaline CaO and the liquid fraction of digestate(LFD)were used as pretreatment agents of rice straw.The results showed that AD performance of rice stra...To improve anaerobic digestion(AD)efficiency of rice straw,solid alkaline CaO and the liquid fraction of digestate(LFD)were used as pretreatment agents of rice straw.The results showed that AD performance of rice straw with CaOLFD pretreatment was optimal in different pretreatment methods of the CaO+LFD,CaOLFD,LFD+CaO,CaO,and LFD.The maximum methane yield(314 ml(g VS)^(-1))and the highest VFAs concentration(14851 mg·L^(-1) on day 3)of the CaOLFD pretreatment group were 81%and 118%higher than that of the control group,respectively.Under the action of solid alkaline CaO,the bacteria of Clostridium,Atopostipes,Sphaerochaeta,Tissierella,Thiopseudomonas,Rikenellaceae,and Sedimentibacter could build up co-cultures with the archaeal of Methanosaeta,Methanobacterium,and Methanosarcina performing direct interspecies electron transfer(DIET)and improving AD performance of rice straw.Therefore,the combined pretreatment using CaO and LFD could not only pretreat rice straw but also stimulate co-cultures of microorganism to establish DIET enhancing AD efficiency.展开更多
The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(P...The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(PtNi_(2))have an enhanced HOR activity compared with single component Pt catalyst.While,the interface electron-transfer kinetics of PtNi_(2)catalyst exhibits a very wide electron-transfer speed distribution.When combined with carbon dots(CDs),the interface charge transfer of PtNi_(2)-CDs composite is optimized,and then the PtNi_(2)-5 mg CDs exhibits about 2.67 times and 4.04 times higher mass and specific activity in 0.1 M KOH than that of 20%commercial Pt/C.In this system,CDs also contribute to trapping H^(+)and H_(2)O generated during HOR,tuning hydrogen binding energy(HBE),and regulating interface electron transfer.This work provides a deep understanding of the interface catalytic kinetics of Pt-based alloys towards highly efficient HOR catalysts design.展开更多
Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epox...Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).展开更多
DFT/6-311+g** level calculations are performed to study the electron transfer bond-breaking reaction of CH3-X. The calculated values are in good agreement with the experimental results or the empirical model. Through ...DFT/6-311+g** level calculations are performed to study the electron transfer bond-breaking reaction of CH3-X. The calculated values are in good agreement with the experimental results or the empirical model. Through analyzing the change of the energy and the charge density along the reaction path, the bond-breaking in ET reaction for CH3X is investigated.展开更多
Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO_(2).A possible solution for the transport of H_(2)in a safe and low-cost way is in the fo...Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO_(2).A possible solution for the transport of H_(2)in a safe and low-cost way is in the form of liquid organic hydrogen carriers(LOHCs).As an alternative to loading LOHC with H_(2)via a two-step procedure involving preliminary electrolytic production of H_(2)and subsequent chemical hydrogenation of the LOHC,we explore here the possibility of electrochemical hydrogen storage(EHS)via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC(R)via a protoncoupled electron transfer(PCET)reaction:2nH^(+)+2ne^(-)+Rox■n H_(2)^(0)Rred.We chose 9-fluorenone/fluorenol(Fnone/Fnol)conversion as such a model PCET reaction.The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity,which enabled us to both quantify and get the mechanistic insight on PCET.The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.展开更多
Cost-effective 3d transition metal(TM) based single atom catalysts(SACs) for oxygen reduction reaction(ORR) are potential alternatives for Pt-based electrocatalysts in fuel cells and metal-air batteries.Understanding ...Cost-effective 3d transition metal(TM) based single atom catalysts(SACs) for oxygen reduction reaction(ORR) are potential alternatives for Pt-based electrocatalysts in fuel cells and metal-air batteries.Understanding the effects of SACs’ properties and active site composition on the catalytic performance is significant to construct highly efficient catalysts. Here, we successfully promote the activity of cobalt single atoms decorated on N-doped carbon nanosheets via tuning the content of different nitrogen components, which outperforms most reported cobalt SACs. The activity and kinetics show positive correlation trends with the content of Co-Nxand graphitic N, serving as the main active sites.Furthermore, ORR kinetics in alkaline media can be positively affected by the conductivity of catalysts while no similar relation is observed in acidic media. The slight loss of Co-Nxsites engenders a mild change of performance in alkaline media, while the decrease of Co-Nxsite activity due to chemical oxidation of carbon support and the loss of Co-Nxsites in acidic media exacerbate the degradation of performance. Our work provides an insight into the relation between ORR electron transfer kinetics and active sites in 3d TM based SACs.展开更多
Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling bio...Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo_(12-n)Vn pretreatment that causes deconstruction of cell wall structure with PMo_(12-n)Vn being simultaneously reduced can be considered as the "charging" process.The reduced PMo_(12-n)Vn are further re-oxidized with release of electrons in a liquid flow fuel cell(LFFC) to generate electricity is the "discharging" process.Several Keggin-type PMo_(12-n)Vn with different degree of vanadium substitution(DSV, namely n) were prepared.Compared to Keggin-type phosphomolybdic acid(PMo_(12)),PMo_(12-n)Vn(n=1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo_(12-n)Vn pretreated wheat straw generally decreased with increase in DSV, but xylan enzymatic digestibility generally increased with DSV.PMo_(12) pretreatment of wheat straw at 120℃ obtained the highest enzymatic glucan conversion(EGC) reaching 95%,followed by PMo11V1 pretreatment(85%).Discharging of the reduced heteropolyacids in LFFC showed that vanadium substitution could improve the maximum output power density(Pmax).The highest Pmax was obtained by PMo9 V3(44.7 mW/cm^(2)) when FeCl_(3) was used as a cathode electron carrier,while PMo_(12) achieved the lowest Pmax(27.4 mW/cm^(2)).All the heteropolyacids showed good electrode Faraday efficiency(>95%) and cell discharging efficiency(>93%).The energy efficiency of the coupled process based on the heat values of the products and generated electric energy was in the range of 18%-25% depending on DSV.PMo_(12) and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.展开更多
Using the innovative method of the additional Bloch vector,the electron transfer properties of a double quantum dot(DQD) system measured by a quantum point contact(QPC) in a fluctuating environment are investigated.Th...Using the innovative method of the additional Bloch vector,the electron transfer properties of a double quantum dot(DQD) system measured by a quantum point contact(QPC) in a fluctuating environment are investigated.The results show that the environmental noises in transverse and longitudinal directions play different roles in the dynamical evolution of the open quantum systems.Considering the DQD with symmetric energy level,the Fano factor exhibits a slight peak with the increase of transverse noise amplitude σ_(T),which provides a basis for distinguishing dynamical phenomena caused by different directional fluctuation noises in symmetric DQD structures by studying the detector output.In the case of asymmetric DQD,the dependence of a detector current involving the level displacement is distinct when increasing the transverse noise damping coefficient τ_(T) and the longitudinal noise damping coefficient τ_(ε) respectively.Meanwhile,the transverse noise damping coefficient τ_(T) could significantly reduce the Fano factor and enhance the stability of the quantum system compared with the longitudinal one.The Fano factors with stable values as the enhancement of noise amplitudes show different external influences from the detector measurement,and provide a numerical reference for adjusting the noise amplitudes in both transverse and longitudinal directions appropriately in a microscopic experimental process to offset the decoherence effect caused by the measurements.Finally,the research of average waiting time provides unique insights to the development of single electron transfer theory in the short-time limit.展开更多
One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance...One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_(3) NH_(3) PbI_(3)(N-MAPbI_(3))/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_(3) NH_(3) PbI_(3)(C-MAPbI_(3))/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_(3), N-MAPbI_(3)/PCBM,C-MAPbI_(3), and C-MAPbI_(3)/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_(3)/PCBM interface is less efficient than that at C-MAPbI_(3)/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_(3)/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm^(-3)–4.0 × 1018 cm^(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10^(18) cm^(-3)–2.2 × 10^(18) cm^(-3).展开更多
In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic so...In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic solvation potentials analysis,we reexamine Marcus’formula with respect to the Rice-Ramsperger-Kassel-Marcus(RRKM)theory.Interestingly,the obtained RRKM analogue,which recovers the original Marcus’rate that is in a linear solvation scenario,is also applicable to the nonlinear solvation scenarios,where the multiple curve-crossing of solvation potentials exists.Parallelly,we revisit the corresponding Fermi’s golden rule results,with some critical comments against the RRKM analogue proposed in this work.For illustration,we consider the quadratic solvation scenarios,on the basis of physically well-supported descriptors.展开更多
The microscopic moleeular theory for electron transfer in a model solvent ishahr developed. The nonlinear response of the solvent molecules is be computedquanitatively in a new way. Adopting computer simulation daa an...The microscopic moleeular theory for electron transfer in a model solvent ishahr developed. The nonlinear response of the solvent molecules is be computedquanitatively in a new way. Adopting computer simulation daa and choosingappropriate reaction coordinae, a reasonable free energy dinram is constructed and thercorganhaion energy for the product state is calculated.展开更多
The photocatalytic activity of CdS can be greatly improved by co-modification of NiS and TiO_2 materials; furthermore the order of connection affects much. A directional electron transfer route via CdS → TiO_2→ NiS ...The photocatalytic activity of CdS can be greatly improved by co-modification of NiS and TiO_2 materials; furthermore the order of connection affects much. A directional electron transfer route via CdS → TiO_2→ NiS is found crucial to the enhancement of ternary catalyst, where TiO_2 acts as an electron reservoir and Ni S works as an effective cocatalyst. Cd S/TiO_2@Ni S with Ni S loaded on TiO_2 has an activity of H_2 evolution 2.5 times higher than NiS@Cd S/TiO_2 with Ni S pre-loaded on Cd S. Faster e-/h+separation rates is obtained of Cd S/TiO_2@Ni S under visible light than under extra UV light irradiation, which in turn demonstrates the importance of directional electron transfer route.展开更多
The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the singl...The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.展开更多
基金supported by the National Key R&D Program of China (2020YFA0710000)the National Natural Science Foundation of China (22278307, 22008170, 21978200, 22161142002, and 22121004)+2 种基金the Applied Basic Research Program of Qinghai Province (2023-ZJ-701)the Haihe Laboratory of Sustainable Chemical Transformationsthe Tianjin Research Innovation Project for Postgraduate Students (2022BKYZ035)。
文摘Sluggish reaction kinetics of oxygen evolution reaction(OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe_(2-x)Ni_xO_(4)(0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic(FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni^(3+)increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe_(1.6)Ni_(0.4)O_(4) shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe_(2)O_(4) and unactivated ZnFe_(1.6)Ni_(0.4)O_(4), and even superior to the benchmark IrO_(2) under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe_(2)O_(4). We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.
基金supported by the National Natural Science Foundation of China(No.2187817622178197)。
文摘Conventional chemical oxidation of aldehydes such as furfural to corresponding acids by molecular oxygen usually needs high pressure to increase the solubility of oxygen in aqueous phase,while electrochemical oxidation needs input of external electric energy.Herein,we developed a liquid flow fuel cell(LFFC)system to achieve oxidation of furfural in anode for furoic acid production with co-production of hydrogen gas.By controlling the electron transfer in cathode for reduction of oxygen,efficient generation of electricity or production of H_(2)O_(2)were achieved.Metal oxides especially Ag_(2)O have been screened as the efficient catalyst to promote the oxidation of aldehydes,while liquid redox couples were used for promoting the kinetics of oxygen reduction.A novel alkaline-acidic asymmetric design was also used for anolyte and catholyte,respectively,to promote the efficiency of electron transfer.Such an LFFC system achieves efficient conversion of chemical energy of aldehyde oxidation to electric energy and makes full use the transferred electrons for high-value added products without input of external energy.With(VO_(2))_(2)SO_(4)as the electron carrier in catholyte for four-electron reduction of oxygen,the peak output power density(Pmax)at room temperature reached 261 mW/cm^(2)with furoic acid and H_(2)yields of 90%and 0.10 mol/mol furfural,respectively.With anthraquinone-2-sulfonate(AQS)as the cathodic electron carrier,Pmaxof 60 mW/cm^(2)and furoic acid,H_(2)and H_(2)O_(2)yields of 0.88,0.15 and 0.41 mol/mol furfural were achieved,respectively.A new reaction mechanism on furfural oxidation on Ag_(2)O anode was proposed,referring to one-electron and two-electron reaction pathways depending on the fate of adsorbed hydrogen atom transferred from furfural aldehyde group.
基金The National Key Research and Development Program of China(2021YFA1502000 and 2022YFA1505300)the National Natural Science Foundation of China (22288102, 22072124)+1 种基金support from Beijing Synchrotron Radiation Facility (1W1B, BSRF)China Scholarship Council for the financial support。
文摘With tunable local electronic environment,high mass density of MN4sites,and ease of preparation,metal-organic conjugated coordinative polymer(CCP) with inherent electronic conductivity provides a promising alternative to the well-known M-N-C electrocatalysts.Herein,the coordination reaction between Cu^(2+)and 1,2,4,5-tetraaminobenzene(TAB) was conducted on the surface of metallic Cu nanowires,forming a thin layer of CuN4-based CCP(Cu-TAB) on the Cu nanowire.More importantly,interfacial transfer of electrons from Cu core to the CuN4-based CCP nanoshell was observed within the resulting CuTAB@Cu,which was found to enrich the local electronic density of the CuN4sites.As such,the CuTAB@Cu demonstrates much improved affinity to the*COOH intermediate formed from the rate determining step;the energy barrier for C-C coupling,which is critical to convert CO_(2)into C2products,is also decreased.Accordingly,it delivers a current density of-9.1 mA cm^(-2)at a potential as high as 0.558 V(vs.RHE) in H-type cell and a Faraday efficiency of 46.4% for ethanol.This work emphasizes the profound role of interfacial interaction in tuning the local electronic structure and activating the CuN4-based CCPs for efficient electroreduction of CO_(2).
基金financial support from the National Natural Science Foundation of China(Grant Nos.51973240,51833011 and 52003303)the China Postdoctoral Science Foundation(Grant Nos.2019M653176 and 2020M672932)+2 种基金the Guang-dong Provincial Basic and Applied Basic Research Fund Natural Science Foundation(Grant No.2020A1515111095)the Fundamental Research Funds for the Central Universities(Grant No.191-gpy117)the Guangdong YangFan Innovative&Entrepreneurial Research Team Program(Grant No.2016YT03C077)。
文摘Searching new structured black phosphorus(BP)and exploring intriguing functions and applications have become a hot topic so far.Here,we introduce a novel Iso-type black phosphorus heterostructure guided by first principle calculation,which features unique heterointerface and electronic coupling interaction via stacking assembly of exfoliated black phosphorus(EBP)and amine-functionalized EBP(N-EBP).Inspired by the theoretical results,we constructed the Iso-type heterostructure comprising of ultrathin exfoliated few-layered EBP and N-EBP,both of which were derived from identical bulk BP.The purposive amine-functionalization not only creates positively-charged P atoms on N-EBP as effective active sites via N-induced intramolecular electron transfer(IET)but also endows N-EBP with lower work function relative to EBP,while the unique EBP/N-EBP Iso-type heterostructure engenders directional heterointerfacial electron transfer(HET).The coupled IET/HET effects optimize the charge redistribution to afford favorable O_(2)adsorption.In this case,our unique strategy for the first time exploits the inherent catalytic capability of BP toward the oxygen reduction reaction(ORR)and enables the first use of BP as metal-free ORR catalysts for Zn-air cells.The newly-designed heterostructure facilitates a 4-e^(-)transfer ORR relative to inactive EBP or N-EBP.Importantly,the polymer-shielded heterostructure acts as efficient air electrodes to endow a primary Zn-air cell with high stability,large capacity and high energy density—superior to the commercial Pt/C-enabled cell.This study as the first report on metal-free BP-based ORR catalysts and air electrodes not only extends BP's application scopes but also renders new insight toward design of electronically-coupled superstructures for energy-related applications.
基金supported by the National Key Research&Development Program of Ministry of Science and Technology of the People’s Republic of China(grant number 2018YFC1900901).
文摘To improve anaerobic digestion(AD)efficiency of rice straw,solid alkaline CaO and the liquid fraction of digestate(LFD)were used as pretreatment agents of rice straw.The results showed that AD performance of rice straw with CaOLFD pretreatment was optimal in different pretreatment methods of the CaO+LFD,CaOLFD,LFD+CaO,CaO,and LFD.The maximum methane yield(314 ml(g VS)^(-1))and the highest VFAs concentration(14851 mg·L^(-1) on day 3)of the CaOLFD pretreatment group were 81%and 118%higher than that of the control group,respectively.Under the action of solid alkaline CaO,the bacteria of Clostridium,Atopostipes,Sphaerochaeta,Tissierella,Thiopseudomonas,Rikenellaceae,and Sedimentibacter could build up co-cultures with the archaeal of Methanosaeta,Methanobacterium,and Methanosarcina performing direct interspecies electron transfer(DIET)and improving AD performance of rice straw.Therefore,the combined pretreatment using CaO and LFD could not only pretreat rice straw but also stimulate co-cultures of microorganism to establish DIET enhancing AD efficiency.
基金supported by the National Key R&D Program of China(2020YFA0406104,2020YFA0406101)the National MCF Energy R&D Program of China(2018YFE0306105)+5 种基金the Innovative Research Group Project of the National Natural Science Foundation of China(51821002)the National Natural Science Foundation of China(51725204,21771132,51972216,52041202)the Natural Science Foundation of Jiangsu Province(BK20190041)the Key-Area Research and Development Program of Guang Dong Province(2019B010933001)the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 Project。
文摘The regulation of interface electron-transfer and catalytic kinetics is very important to design the efficient electrocatalyst for alkaline hydrogen oxidation reaction(HOR).Here,we show the Pt-Ni alloy nanoparticles(PtNi_(2))have an enhanced HOR activity compared with single component Pt catalyst.While,the interface electron-transfer kinetics of PtNi_(2)catalyst exhibits a very wide electron-transfer speed distribution.When combined with carbon dots(CDs),the interface charge transfer of PtNi_(2)-CDs composite is optimized,and then the PtNi_(2)-5 mg CDs exhibits about 2.67 times and 4.04 times higher mass and specific activity in 0.1 M KOH than that of 20%commercial Pt/C.In this system,CDs also contribute to trapping H^(+)and H_(2)O generated during HOR,tuning hydrogen binding energy(HBE),and regulating interface electron transfer.This work provides a deep understanding of the interface catalytic kinetics of Pt-based alloys towards highly efficient HOR catalysts design.
基金supported by the Natural Science Foundation of China(21978325,21776312,22078364)Key research and development plan of Shandong Province(2019RKE28003,2018GGX107005)Fundamental Research Funds for the Central Universities(18CX02014A).
文摘Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).
文摘DFT/6-311+g** level calculations are performed to study the electron transfer bond-breaking reaction of CH3-X. The calculated values are in good agreement with the experimental results or the empirical model. Through analyzing the change of the energy and the charge density along the reaction path, the bond-breaking in ET reaction for CH3X is investigated.
基金financially supported by the Swedish Research Council(grant 2016-05990)the Knut and Alice Wallenberg Foundation(H2O2 and Cellfion)the Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Link?ping University(Faculty Grant SFO-Mat-Li U No.200900971)。
文摘Green hydrogen is identified as one of the prime clean energy carriers due to its high energy density and a zero emission of CO_(2).A possible solution for the transport of H_(2)in a safe and low-cost way is in the form of liquid organic hydrogen carriers(LOHCs).As an alternative to loading LOHC with H_(2)via a two-step procedure involving preliminary electrolytic production of H_(2)and subsequent chemical hydrogenation of the LOHC,we explore here the possibility of electrochemical hydrogen storage(EHS)via conversion of proton of a proton donor into a hydrogen atom involved in covalent bonds with the LOHC(R)via a protoncoupled electron transfer(PCET)reaction:2nH^(+)+2ne^(-)+Rox■n H_(2)^(0)Rred.We chose 9-fluorenone/fluorenol(Fnone/Fnol)conversion as such a model PCET reaction.The electrochemical activation of Fnone via two sequential electron transfers was monitored with in-situ and operando spectroscopies in absence and in presence of different alcohols as proton donors of different reactivity,which enabled us to both quantify and get the mechanistic insight on PCET.The possibility of hydrogen extraction from the loaded carrier molecule was illustrated by chemical activation.
基金financial support from the Natural Science Foundation of Beijing Municipality (2191001)the National Natural Science Foundation of China (51631001, 51672010 and 52001007)+1 种基金the National Key R&D Program of China(2017YFA0206301)the China Postdoctoral Science Foundation (2020M670038)。
文摘Cost-effective 3d transition metal(TM) based single atom catalysts(SACs) for oxygen reduction reaction(ORR) are potential alternatives for Pt-based electrocatalysts in fuel cells and metal-air batteries.Understanding the effects of SACs’ properties and active site composition on the catalytic performance is significant to construct highly efficient catalysts. Here, we successfully promote the activity of cobalt single atoms decorated on N-doped carbon nanosheets via tuning the content of different nitrogen components, which outperforms most reported cobalt SACs. The activity and kinetics show positive correlation trends with the content of Co-Nxand graphitic N, serving as the main active sites.Furthermore, ORR kinetics in alkaline media can be positively affected by the conductivity of catalysts while no similar relation is observed in acidic media. The slight loss of Co-Nxsites engenders a mild change of performance in alkaline media, while the decrease of Co-Nxsite activity due to chemical oxidation of carbon support and the loss of Co-Nxsites in acidic media exacerbate the degradation of performance. Our work provides an insight into the relation between ORR electron transfer kinetics and active sites in 3d TM based SACs.
基金supported by the National Key Research and Development Program of China(2018YFA0902200)the National Natural Science Foundation of China(No.21878176)。
文摘Owing to their acidity,oxidizing ability and redox reversibility,molybdovanadophosphoric heteropolyacids(H_(n+3)PMo_(12-n)VnO40,abbreviated as PMo_(12-n)Vn) were employed as electron transfer carriers for coupling biomass pretreatment for enzymatic hydrolysis and direct biomass-to-electricity conversion.In this novel coupled process,PMo_(12-n)Vn pretreatment that causes deconstruction of cell wall structure with PMo_(12-n)Vn being simultaneously reduced can be considered as the "charging" process.The reduced PMo_(12-n)Vn are further re-oxidized with release of electrons in a liquid flow fuel cell(LFFC) to generate electricity is the "discharging" process.Several Keggin-type PMo_(12-n)Vn with different degree of vanadium substitution(DSV, namely n) were prepared.Compared to Keggin-type phosphomolybdic acid(PMo_(12)),PMo_(12-n)Vn(n=1-6) showed higher oxidizing ability but poorer redox reversibility.The cellulose enzymatic digestibility of PMo_(12-n)Vn pretreated wheat straw generally decreased with increase in DSV, but xylan enzymatic digestibility generally increased with DSV.PMo_(12) pretreatment of wheat straw at 120℃ obtained the highest enzymatic glucan conversion(EGC) reaching 95%,followed by PMo11V1 pretreatment(85%).Discharging of the reduced heteropolyacids in LFFC showed that vanadium substitution could improve the maximum output power density(Pmax).The highest Pmax was obtained by PMo9 V3(44.7 mW/cm^(2)) when FeCl_(3) was used as a cathode electron carrier,while PMo_(12) achieved the lowest Pmax(27.4 mW/cm^(2)).All the heteropolyacids showed good electrode Faraday efficiency(>95%) and cell discharging efficiency(>93%).The energy efficiency of the coupled process based on the heat values of the products and generated electric energy was in the range of 18%-25% depending on DSV.PMo_(12) and PMo11V1 seem to be the most suitable heteropolyacids to mediate the coupled process.
基金Project supported by the Natural Science Foundation of Shandong Province,China(Grant No.ZR2014AM030)。
文摘Using the innovative method of the additional Bloch vector,the electron transfer properties of a double quantum dot(DQD) system measured by a quantum point contact(QPC) in a fluctuating environment are investigated.The results show that the environmental noises in transverse and longitudinal directions play different roles in the dynamical evolution of the open quantum systems.Considering the DQD with symmetric energy level,the Fano factor exhibits a slight peak with the increase of transverse noise amplitude σ_(T),which provides a basis for distinguishing dynamical phenomena caused by different directional fluctuation noises in symmetric DQD structures by studying the detector output.In the case of asymmetric DQD,the dependence of a detector current involving the level displacement is distinct when increasing the transverse noise damping coefficient τ_(T) and the longitudinal noise damping coefficient τ_(ε) respectively.Meanwhile,the transverse noise damping coefficient τ_(T) could significantly reduce the Fano factor and enhance the stability of the quantum system compared with the longitudinal one.The Fano factors with stable values as the enhancement of noise amplitudes show different external influences from the detector measurement,and provide a numerical reference for adjusting the noise amplitudes in both transverse and longitudinal directions appropriately in a microscopic experimental process to offset the decoherence effect caused by the measurements.Finally,the research of average waiting time provides unique insights to the development of single electron transfer theory in the short-time limit.
基金supported by the National Natural Science Foundation of China (Grant Nos. 21503066 and 61904048)the Fundamental Research Project from Shenzhen Science and Technology Innovation Committee (Grant No. JCYJ20180302174021198)+2 种基金the Natural Science Foundation of Hebei ProvinceChina(Grant No. F2017201136)the Foundation of Hebei Educational Committee (Grant No. ZC2016003)。
文摘One-dimensional nanowire is an important candidate for lead-halide perovskite-based photonic detectors and solar cells. Its surface population, diameter, and growth direction, etc., are critical for device performance. In this research,we carried out a detailed study on electron transfer process at the interface of nanowire CH_(3) NH_(3) PbI_(3)(N-MAPbI_(3))/Phenyl C61 butyric acid methyl-ester synonym(PCBM), as well as the interface of compact CH_(3) NH_(3) PbI_(3)(C-MAPbI_(3))/PCBM by transient absorption spectroscopy. By comparing the carrier recombination dynamics of N-MAPbI_(3), N-MAPbI_(3)/PCBM,C-MAPbI_(3), and C-MAPbI_(3)/PCBM from picosecond(ps) to hundred nanosecond(ns) time scale, it is demonstrated that electron transfer at N-MAPbI_(3)/PCBM interface is less efficient than that at C-MAPbI_(3)/PCBM interface. In addition, electron transfer efficiency at C-MAPbI_(3)/PCBM interface was found to be excitation density-dependent, and it reduces with photo-generation carrier concentration increasing in a range from 1.0 × 1018 cm^(-3)–4.0 × 1018 cm^(-3). Hot electron transfer,which leads to acceleration of electron transfer between the interfaces, was also visualized as carrier concentration increases from 1.0 × 10^(18) cm^(-3)–2.2 × 10^(18) cm^(-3).
基金This work was supported by the Ministry of Science and Technology of China(No.2017YFA0204904 and No.2016YFA0400904)the National Natural Science Foundation of China(No.21633006),and Anhui Initiative in Quantum Information Technologies.
文摘In the pioneering work by R.A.Marcus,the solvation effect on electron transfer(ET)processes was investigated,giving rise to the celebrated nonadiabatic ET rate formula.In this work,on the basis of the thermodynamic solvation potentials analysis,we reexamine Marcus’formula with respect to the Rice-Ramsperger-Kassel-Marcus(RRKM)theory.Interestingly,the obtained RRKM analogue,which recovers the original Marcus’rate that is in a linear solvation scenario,is also applicable to the nonlinear solvation scenarios,where the multiple curve-crossing of solvation potentials exists.Parallelly,we revisit the corresponding Fermi’s golden rule results,with some critical comments against the RRKM analogue proposed in this work.For illustration,we consider the quadratic solvation scenarios,on the basis of physically well-supported descriptors.
文摘The microscopic moleeular theory for electron transfer in a model solvent ishahr developed. The nonlinear response of the solvent molecules is be computedquanitatively in a new way. Adopting computer simulation daa and choosingappropriate reaction coordinae, a reasonable free energy dinram is constructed and thercorganhaion energy for the product state is calculated.
基金Supported by the Scientific Research Starting Foundation for Doctors(trxyD H1512)the Foundation for Youth Talent Growth Project in the Ministry of Science and Technology of China(20171184)the Mutual Foundation in the Ministry of Science and Technology of China(20177315)
文摘The photocatalytic activity of CdS can be greatly improved by co-modification of NiS and TiO_2 materials; furthermore the order of connection affects much. A directional electron transfer route via CdS → TiO_2→ NiS is found crucial to the enhancement of ternary catalyst, where TiO_2 acts as an electron reservoir and Ni S works as an effective cocatalyst. Cd S/TiO_2@Ni S with Ni S loaded on TiO_2 has an activity of H_2 evolution 2.5 times higher than NiS@Cd S/TiO_2 with Ni S pre-loaded on Cd S. Faster e-/h+separation rates is obtained of Cd S/TiO_2@Ni S under visible light than under extra UV light irradiation, which in turn demonstrates the importance of directional electron transfer route.
文摘The SET mechanism between chlorine dioxide （ClO2） and phenol was studied by using ab initio method at 4-31G* level. Geometries of the reactants, intermediate and products of the reaction were optimized and the single point energy calculations of the species were performed. The relative structure data of the reactants, intermediate and products are given.The SET mechanism between ClO2and phenol was confirmed by ab initio calculations. The reaction is exothermic about 200 88 kJ/mol.
