Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strat...Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strategy of NiCoP/S nanocrystals(NCs) was proposed through using seed crystal conversion approach with NiCo_(2)S_(4) spinel as precursor. The small amount of S atoms in NiCoP/S NCs perturbed the local electronic structure, leading to the atomic position shift of the nearest neighbor in the protocell and the nanoscale lattice strain, which optimized the H* adsorption free energy and activated H_(2)O molecules, resulting the dramatically elevated HER performance within a wide p H range. Especially, the NiCoP/S NCs displayed better HER electrocatalytic activity than comical 20% Pt/C at high current density in 1 M KOH and natural seawater: it only needed 266 m V vs. reversible hydrogen electrode(RHE) and660 m V vs. RHE to arrive the current density of 350 m A cm^(-2) in 1 M KOH and natural seawater, indicating the application prospect for industrial high current. Besides, NiCoP/S NCs also displayed excellent supercapacitor performance: it showed high specific capacity of 2229.9 F g^(-1) at 1 A g^(-1) and energy density of87.49 Wh kg^(-1), when assembled into an all-solid-state flexible device, exceeding performance of most transition metal phosphides. This work provides new insights into the regulation in electronic structure and lattice strain for electrocatalytic and energy storage applications.展开更多
Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen ...Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.展开更多
Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO5...Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of1774.3 m^2/g. Heteroatom-doped porous carbon(PC) was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs.reversible hydrogen electrode(RHE). This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom(N,S) content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources.展开更多
The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.E...The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.展开更多
Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated ...Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated WP_(2) self-supporting nanosheet arrays cathode was synthesized on carbon cloth(Ni-WP_(2) NS/CC)by in-situ phosphating reduction of the Ni-doped WO3.It shows that heteroatom doping and the three-dimensional(3D)nanosheet arrays morphology both facilitate to reduce the interfacial transfer resistance and increase electrochemical-active surface areas,which effectively improve electrocatalytic hydrogen evolution reaction(HER)activity.The optimized catalyst,1%Ni-WP_(2) NS/CC,exhibits an outstanding electrocatalytic performance with an overpotential of 110 m V at 10 m A cm^(-2) and a Tafel slope of 65 m V dec^(-1) in the acid solution.DFT calculations further demonstrate the nickel doping can adjust the intrinsic structure of electronics,lower the Gibbs free energy of adsorption of hydrogen(DGH*),and effectively improve the HER performance.展开更多
Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HD...Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.展开更多
The large-scale application of sodium ion batteries(SIBs)is limited by economic and environmental factors.Here,we prepare multi-heteroatom self-doped hierarchical porous carbon(HHPC)with a honeycomb-like structure by ...The large-scale application of sodium ion batteries(SIBs)is limited by economic and environmental factors.Here,we prepare multi-heteroatom self-doped hierarchical porous carbon(HHPC)with a honeycomb-like structure by one-step carbonization method using high-yield and low-cost biomass silkworm excrement as a precursor.As an anode for SIB,HHPC-1100 exhibits a capacity of 331.7 mA h g^(-1) at 20 mA g^(-1),while it also reveals remarkable rate performance and stable long cycle capability due to its abundant pore structure and proper amount of hetero atom doping.Moreover,the synergistic effect of O,N,S,P co-doping in carbon materials on sodium ion adsorption is verified by the first-principles study,which provide a theoretical basis for the prominent electrochemical performance of the material.展开更多
Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-d...Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-doped Ni_(2)P catalyst as a research model and found that the introduction of heterogeneous Co reconstructed the charge distribution around the P site,which effectively enhanced the hydrogen evolution reaction(HER)activity of the pure Ni_(2)P.Based on in-situ Raman real-time monitoring technology,we monitored for the first time that Co doping triggered a switch of the active site(from the original Co-active site to the P-active site),which promoted the adsorption of H_(2)O to enhance the HER activity.The density functional theory(DFT)calculations indicated that the P site of Co-Ni_(2)P expressed the highest activity and the Ni site of pure Ni_(2)P expressed the highest activity,which further confirms the in-situ Raman monitoring results.The active site turnover mechanism discovered in this study will undoubtedly provide more rational and targeted ideas for future catalyst design.展开更多
Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low...Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.展开更多
Metal-free, heteroatom functionalized carbon-based catalysts have made remarkable progress in recent years in a wide range of applications related to energy storage and energy generation. In this study, high surface a...Metal-free, heteroatom functionalized carbon-based catalysts have made remarkable progress in recent years in a wide range of applications related to energy storage and energy generation. In this study, high surface area mesoporous ordered sulphur doped carbon materials are obtained via one-pot hydrothermal synthesis of carbon/SBA-15 composite after removal of in-situ synthesized hard template SiO2. 2-thiophenecarboxy acid as sulphur source gives rise to sulphur doping level of 5.5 wt%. Comparing with pristine carbon, the sulphur doped mesoporous ordered carbon demonstrates improved electro-catalytic activity in the oxygen reduction reaction in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.展开更多
the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent p...the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.展开更多
Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and sma...Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.展开更多
Hydrogen peroxide (H_(2)O_(2)) is a valuable chemical for a wide variety of applications. The environmentally friendly production route of the electrochemical reduction of O_(2)to H_(2)O_(2) has become an attractive a...Hydrogen peroxide (H_(2)O_(2)) is a valuable chemical for a wide variety of applications. The environmentally friendly production route of the electrochemical reduction of O_(2)to H_(2)O_(2) has become an attractive alternative to the traditional anthraquinone process. The efficiency of electrosynthesis process depends considerably on the availability of cost-effective catalysts with high selectivity, activity, and stability.Currently, there are many outstanding issues in the preparation of highly selective catalysts, the exploration of the interface electrolysis environment, and the construction of electrolysis devices, which have led to extensive research efforts. Distinct from the existing few comprehensive review articles on H_(2)O_(2) production by two-electron oxygen reduction, the present review first explains the principle of the oxygen reduction reaction and then highlights recent advances in the regulation and control strategies of different types of catalysts. Key factors of electrode structure and device design are discussed. In addition,we highlight the promising co-production combination of this system with renewable energy or energy storage systems. This review can help introduce the potential of oxygen reduction electrochemical production of high-flux H_(2)O_(2) to the commercial market.展开更多
Attracted by high energy density and considerable conductivity of selenium(Se),Na-Se batteries have been deemed promising energy-storage systems.But,it still suffers from sluggish kinetic behaviors and similar“shuttl...Attracted by high energy density and considerable conductivity of selenium(Se),Na-Se batteries have been deemed promising energy-storage systems.But,it still suffers from sluggish kinetic behaviors and similar“shuttling effect”to S-electrodes.Herein,utilizing uniform hollow carbon spheres as precursors,Se-material is effectively loaded through vapor-infiltration method.Owing to the distribution of optimized pores,the content of microspores could be up to~60%(<2 nm),serving important roles for the physical confinement effect.Meanwhile,the rich oxygen-containing groups and N-elements could be noted,inducing the evolution of electron-moving behaviors.More significantly,assisted by the interfacial C-Se bonds and tiny Se distributions,Se electrodes are activated during cycling.Used as cathodes for Na-Se systems,the as-resulted samples display a capacity of 593.9 mA h g^(-1)after 100 cycles at the current density of 0.1 C.Even after 6000 cycles,the capacity could be still kept at about 225 mA h g^(-1)at 5.0 C.Supported by the detailed kinetic analysis,the designed microspores size induces the increasing redox reaction of nano Se,whilst the surface traits further render the enhancement of pseudo-capacitive contributions.Moreover,after cycling,the product Sex(x<4)in pores serves as the primary active material.Given this,the work is anticipated to provide an effective strategy for advanced electrodes for Na-Se systems.展开更多
Introducing heteroatoms and defects is a significant strategy to improve oxygen evolution reaction(OER)performance of electrocatalysts.However,the synergistic interaction of the heteroatom and defect still needs furth...Introducing heteroatoms and defects is a significant strategy to improve oxygen evolution reaction(OER)performance of electrocatalysts.However,the synergistic interaction of the heteroatom and defect still needs further investigations.Herein,we demonstrated an oxygen vacancy-rich vanadium-doped Co_(3)O_(4)(V-Ov-Co_(3)O_(4)),fabricated by V-ion implantation,could be used for high-efficient OER catalysis.X-ray photoelectron spectra(XPS)and density functional theory(DFT)calculations show that the charge density of Co atom increased,and the reaction barrier of reaction pathway from O∗to HOO∗decreased.V-Ov-Co_(3)O_(4) catalyst shows a low overpotential of 329 mV to maintain current density of 10 mA·cm^(−2),and a small Tafel slope of 74.5 mV·dec^(−1).This modification provides us with valuable perception for future design of heteroatom-doped and defect-based electrocatalysts.展开更多
Highly efficient electrocatalysts towards hydrogen evolution reaction(HER) with large current density at all-pH values are critical for the sustainable hydrogen production. Herein, we report a free-standing HER electr...Highly efficient electrocatalysts towards hydrogen evolution reaction(HER) with large current density at all-pH values are critical for the sustainable hydrogen production. Herein, we report a free-standing HER electrode, phosphorous-doped molybdenum nitride nanoparticles embedded in 3-dimentional carbon nanosheet matrix(P-Mo2N-CNS) fabricated via one-step carbonization and in-situ formation. The asprepared catalyst shows free-standing architecture with interconnected porous microstructure. P-doped Mo2N nanoparticles with an average diameter of 4.4 nm are well embedded in the 3-dimentional vertical carbon nanosheets matrix. Remarkable electrocatalytic HER performance is observed in alkaline, neutral and acidic media at large current densities. The overpotential of P-Mo2N-CNS to drive a current density of 100 mA cm-2 in 0.5 M H2SO4 and 1.0 M PBS is only 181 and 221 mV, respectively. In particular, the current density reaches up to 1000 mA cm-2 at a low overpotential of 256 mV in 1.0 M KOH, much better than that of the commercial Pt/C catalyst. Density functional theory calculations suggest the optimized H sorption kinetics on Mo2N after P doping, elucidating the superior activity.展开更多
The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(EC...The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.展开更多
基金supported by the National Natural Science Foundation of China(22108306,22109090)the Taishan Scholars Program of Shandong Province(tsqn201909065)the Shandong Provincial Natural Science Foundation(ZR2021YQ15,ZR2020QB174)。
文摘Developing high-efficiency multifunctional nanomaterials is promising for wide p H hydrogen evolution reaction(HER) and energy storage but still challenging. Herein, a novel in-situ doping-induced lattice strain strategy of NiCoP/S nanocrystals(NCs) was proposed through using seed crystal conversion approach with NiCo_(2)S_(4) spinel as precursor. The small amount of S atoms in NiCoP/S NCs perturbed the local electronic structure, leading to the atomic position shift of the nearest neighbor in the protocell and the nanoscale lattice strain, which optimized the H* adsorption free energy and activated H_(2)O molecules, resulting the dramatically elevated HER performance within a wide p H range. Especially, the NiCoP/S NCs displayed better HER electrocatalytic activity than comical 20% Pt/C at high current density in 1 M KOH and natural seawater: it only needed 266 m V vs. reversible hydrogen electrode(RHE) and660 m V vs. RHE to arrive the current density of 350 m A cm^(-2) in 1 M KOH and natural seawater, indicating the application prospect for industrial high current. Besides, NiCoP/S NCs also displayed excellent supercapacitor performance: it showed high specific capacity of 2229.9 F g^(-1) at 1 A g^(-1) and energy density of87.49 Wh kg^(-1), when assembled into an all-solid-state flexible device, exceeding performance of most transition metal phosphides. This work provides new insights into the regulation in electronic structure and lattice strain for electrocatalytic and energy storage applications.
基金supported by the National Natural Science Foundation of China(22179065,22111530112,21875118)the Tianjin Graduate Research and Innovation Project(2022BKY018)the Ph.D.Candidate Research Innovation Fund of NKU School of Materials Science and Engineering.
文摘Hydrazine-assisted water electrolysis is a promising energy conversion technology for highly efficient hydrogen production.Rational design of bifunctional electrocatalysts,which can simultaneously accelerate hydrogen evolution reaction(HER)/hydrazine oxidation reaction(HzOR)kinetics,is the key step.Herein,we demonstrate the development of ultrathin P/Fe co-doped NiSe_(2) nanosheets supported on modified Ni foam(P/Fe-NiSe_(2)) synthesized through a facile electrodeposition process and subsequent heat treatment.Based on electrochemical measurements,characterizations,and density functional theory calculations,a favorable“2+2”reaction mechanism with a two-step HER process and a two-step HzOR step was fully proved and the specific effect of P doping on HzOR kinetics was investigated.P/Fe-NiSe_(2) thus yields an impressive electrocatalytic performance,delivering a high current density of 100 mA cm^(−2) with potentials of−168 and 200 mV for HER and HzOR,respectively.Additionally,P/Fe-NiSe_(2) can work efficiently for hydrazine-assisted water electrolysis and Zn-Hydrazine(Zn-Hz)battery,making it promising for practical application.
基金supported by the Doctor Foundation of Bingtuan (No.2014BB004)National Natural Science Foundation of China (U130329)+1 种基金the Program for Changjiang Scholars, Innovative Research Team in University (No. IRT_15R46)the Program of Science and Technology Innovation Team in Bingtuan (No. 2015BD003)
文摘Banana peel-derived porous carbon(BPPC) was prepared from banana peel and used as an adsorbent for methyl orange(MO) wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of1774.3 m^2/g. Heteroatom-doped porous carbon(PC) was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs.reversible hydrogen electrode(RHE). This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom(N,S) content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources.
基金financially supported by the National Natural Science Foundation of China(21972068,21875112,22072067,21878047,22075290 and 21676056)the Qing Lan Project of Jiangsu Province(1107040167)+3 种基金the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX20_0121)the China Scholarship Council(CSC,202006090294)the Fundamental Research Funds for the Central Universities(3207042101D)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)(1107047002)。
文摘The search for non-precious and efficient electrocatalysts towards the oxygen evolution reaction(OER)is of vital importance for the future advancement of multifarious renewable energy conversion/storage technologies.Electronic modulation via heteroatom doping is recognized as one of the most forceful leverages to enhance the electrocatalytic activity.Herein,we demonstrate a delicate strategy for the in-situ confinement of S-doped Ni O nanoparticles into N-doped carbon nanotube/nanofiber-coupled hierarchical branched superstructures(labeled as S-Ni O@N-C NT/NFs).The developed strategy simultaneously combines enhanced thermodynamics via electronic regulation with accelerated kinetics via nanoarchitectonics.The S-doping into Ni O lattice and the 1 D/1 D-integrated hierarchical branched carbon substrate confer the resultant S-Ni O@N-C NT/NFs with regulated electronic configuration,enriched oxygen vacancies,convenient mass diffusion pathways and superior architectural robustness.Thereby,the SNi O@N-C NT/NFs display outstanding OER properties with an overpotential of 277 m V at 10 m A cm^(-2)and impressive long-term durability in KOH medium.Density functional theory(DFT)calculations further corroborate that introducing S-dopant significantly enhances the interaction with key oxygenate intermediates and narrow the band gap.More encouragingly,a rechargeable Zn-air battery using an air-cathode of Pt/C+S-Ni O@N-C NT/NFs exhibits a lower charge voltage and preferable cycling stability in comparison with the commercial Pt/C+Ru O_(2)counterpart.This study highlighting the concurrent consideration of electronic regulation,architectural design and nanocarbon hybridization may shed light on the future exploration of economical and efficient electrocatalysts.
基金supported by the National Natural Science Foundation of China(21503051,21563007)the Natural Science Foundation of Guangxi Province(2019GXNSFFA245016,2018GXNSFAA138108)。
文摘Modulate the electronic structure and surface energy by nanostructure and heteroatom doping is an efficient strategy to improve electrocatalytic activity of hydrogen evolution reaction(HER).Herein,nickel incorporated WP_(2) self-supporting nanosheet arrays cathode was synthesized on carbon cloth(Ni-WP_(2) NS/CC)by in-situ phosphating reduction of the Ni-doped WO3.It shows that heteroatom doping and the three-dimensional(3D)nanosheet arrays morphology both facilitate to reduce the interfacial transfer resistance and increase electrochemical-active surface areas,which effectively improve electrocatalytic hydrogen evolution reaction(HER)activity.The optimized catalyst,1%Ni-WP_(2) NS/CC,exhibits an outstanding electrocatalytic performance with an overpotential of 110 m V at 10 m A cm^(-2) and a Tafel slope of 65 m V dec^(-1) in the acid solution.DFT calculations further demonstrate the nickel doping can adjust the intrinsic structure of electronics,lower the Gibbs free energy of adsorption of hydrogen(DGH*),and effectively improve the HER performance.
基金financial support from the Nankai UniversityNational Science Foundation of China(No.21875119)+1 种基金Natural Science Foundation of Tianjin(19JCYBJC17500)the open fund of the key laboratory of advanced functional polymer materials,the ministry of education(Nankai University,KLFPM202001)。
文摘Electrocatalysts play a crucial role in the development of renewable energy conversion and storage nanotechnologies.The unique advantages of heteroatom-doped porous carbon-supported single-atom electrocatalysts(SAC-HDPCs)are clear.These SAC-HDPCs exhibit outstanding activity,selectivity and stability due to their distinct electronic structure,satisfactory conductivity,controllable porosity and heteroatomdoping effect.Rapid and significant developments involving the synthesis,characterization,and structure-property-function relationship of SAC-HDPCs have been made in recent years.In this review,we describe recent research efforts involving advanced(in situ)characterization techniques,innovative synthetic strategies,and electrochemical energy conversion examples of SAC-HDPCs.The electrocatalytic performance of SAC-HDPCs is further considered at an atomic level,and the mechanisms underlying this performance are also discussed in detail.We expect that these analyses and deductions will be useful for the design of new materials and may help to establish a foundation for the design of future SAC-HDPCs.
基金supported by the National Natural Science Foundation of China(Grant No.51872236)the Joint Fund ProjectEnterprise-Shaanxi Coal Joint Fund Project(2019JLM-32)。
文摘The large-scale application of sodium ion batteries(SIBs)is limited by economic and environmental factors.Here,we prepare multi-heteroatom self-doped hierarchical porous carbon(HHPC)with a honeycomb-like structure by one-step carbonization method using high-yield and low-cost biomass silkworm excrement as a precursor.As an anode for SIB,HHPC-1100 exhibits a capacity of 331.7 mA h g^(-1) at 20 mA g^(-1),while it also reveals remarkable rate performance and stable long cycle capability due to its abundant pore structure and proper amount of hetero atom doping.Moreover,the synergistic effect of O,N,S,P co-doping in carbon materials on sodium ion adsorption is verified by the first-principles study,which provide a theoretical basis for the prominent electrochemical performance of the material.
基金financial support from the National Natural Science Foundation of China(No.52302098,52336003,52176076,51676103)China Postdoctoral Science Foundation(2023M731855)+3 种基金Taishan Scholar Project of Shandong Province(China)(No.ts20190937)Natural Science Foundation of Shandong Province(China)(No.ZR2023QE344,ZR2021LFG003)Qingdao Postdoctoral Science Foundation(No.QDBSH20220201021,QDBSH20220202084)The Youth Innovation Project for Universities of Shandong Province(2023KJ102)。
文摘Although heteroatom doping is an effective way to improve the catalytic activity of transition metal phosphides(TMPs),the mechanism of activity enhancement needs to be further refined.To this end,we synthesized a Co-doped Ni_(2)P catalyst as a research model and found that the introduction of heterogeneous Co reconstructed the charge distribution around the P site,which effectively enhanced the hydrogen evolution reaction(HER)activity of the pure Ni_(2)P.Based on in-situ Raman real-time monitoring technology,we monitored for the first time that Co doping triggered a switch of the active site(from the original Co-active site to the P-active site),which promoted the adsorption of H_(2)O to enhance the HER activity.The density functional theory(DFT)calculations indicated that the P site of Co-Ni_(2)P expressed the highest activity and the Ni site of pure Ni_(2)P expressed the highest activity,which further confirms the in-situ Raman monitoring results.The active site turnover mechanism discovered in this study will undoubtedly provide more rational and targeted ideas for future catalyst design.
基金the National Natural Science Foundation of China(No.21875221,21571157,U1604123,and 21773016)the Youth Talent Support Program of High-Level Talents Special Support Plan in Henan Province(ZYQR201810148)+1 种基金Creative talents in the Education Department of Henan Province(19HASTIT039)the project supported by State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology)(2019-KF-13).
文摘Electrocatalytic carbon dioxide(CO2)reduction(ECR)has become one of the main methods to close the broken carbon cycle and temporarily store renewable energy,but there are still some problems such as poor stability,low activity,and selectivity.While the most promising strategy to improve ECR activity is to develop electrocatalysts with low cost,high activity,and long-term stability.Recently,defective carbon-based nanomaterials have attracted extensive attention due to the unbalanced electron distribution and electronic structural distortion caused by the defects on the carbon materials.Here,the present review mainly summarizes the latest research progress of the construction of the diverse types of defects(intrinsic carbon defects,heteroatom doping defects,metal atomic sites,and edges detects)for carbon materials in ECR,and unveil the structure-activity relationship and its catalytic mechanism.The current challenges and opportunities faced by high-performance carbon materials in ECR are discussed,as well as possible future solutions.It can be believed that this review can provide some inspiration for the future of development of high-performance ECR catalysts.
基金supported by the University of Electronic Science and Technology of China(Y02002010301080)the National Science Foundation of China(51502032)the financial support from Natural Science Foundation of Zhejiang Province(No.LQ14E020003)
文摘Metal-free, heteroatom functionalized carbon-based catalysts have made remarkable progress in recent years in a wide range of applications related to energy storage and energy generation. In this study, high surface area mesoporous ordered sulphur doped carbon materials are obtained via one-pot hydrothermal synthesis of carbon/SBA-15 composite after removal of in-situ synthesized hard template SiO2. 2-thiophenecarboxy acid as sulphur source gives rise to sulphur doping level of 5.5 wt%. Comparing with pristine carbon, the sulphur doped mesoporous ordered carbon demonstrates improved electro-catalytic activity in the oxygen reduction reaction in alkaline solution. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
基金supported by grants from the National Natural Science Foundation of China (Grant Nos. 21573066, 21825201, 2187350, 51402100 and 21905088)。
文摘the types and strategies used to prepare defect electrocatalysts will continue to be studied and developed as new defective materials are generated.4. Characterization of defectsThis review briefly summarizes recent progress in defect electrocatalysts, and the synthesis strategies and characterization techniques for defects are systematically discussed. Although challenges in the characterization of defect structures in the electrocatalytic reaction process remain, the dynamic evolution of defect sites is predicted to be helpful for designing and preparing high-performance electrocatalysts for commercial applications. Furthermore, due to an insufficient understanding of the defect-structureproperty relationships, future possibilities for the reasonable design of defect electrocatalysts to obtain desirable performance are suggested.
基金financial support from the National Nature Science Foundation of China (21971146 and 22105118)the Nature Science Foundation of Shandong Provinces (ZR2021QB095)the China Postdoctoral Science Foundation (2020TQ0183 and 2021M701979)。
文摘Fast charging and high volumetric capacity are two of the critical demands for sodium-ion batteries(SIBs).Although nanostructured materials achieve outstanding rate performance,they suffer from low tap density and small volumetric capacity.Therefore,how to realize large volumetric capacity and high tap density simultaneously is very challenging.Here,N/F co-doped TiO_(2)/carbon microspheres(NF- TiO_(2)/C)are synthesized to achieve both of them.Theoretical calculations reveal that N and F co-doping increases the contents of oxygen vacancies and narrows the bandgaps of TiO_(2) and C,improving the electronic conductivity of NF- TiO_(2)/C.Furthermore,NF- TiO_(2)/C exhibits the high binding energy and low diffusion energy barrier of Na+,significantly facilitating Na+storage and Na+diffusion.Therefore,NF- TiO_(2)/C offers a high tap density(1.51 g cm^(-3)),an outstanding rate performance(125.9 mAh g^(-1) at 100 C),a large volumetric capacity(190 mAh cm^(-3) at 100 C),a high areal capacity(4.8 mAh cm^(-2))and an ultra-long cycling performance(80.2%after 10,000 cycles at 10 C)simultaneously.In addition,NF- TiO_(2)/C||Na_(3)V_(2)(PO_(4))_(3) full cells achieve an ultrahigh power density of 25.2 kW kg^(-1).These results indicate the great promise of NF- TiO_(2)/C as a high-volumetric-capacity and high-power-density anode material of SIBs.
基金supported by the National Natural Science Foundation of China (51702225, 22179089)。
文摘Hydrogen peroxide (H_(2)O_(2)) is a valuable chemical for a wide variety of applications. The environmentally friendly production route of the electrochemical reduction of O_(2)to H_(2)O_(2) has become an attractive alternative to the traditional anthraquinone process. The efficiency of electrosynthesis process depends considerably on the availability of cost-effective catalysts with high selectivity, activity, and stability.Currently, there are many outstanding issues in the preparation of highly selective catalysts, the exploration of the interface electrolysis environment, and the construction of electrolysis devices, which have led to extensive research efforts. Distinct from the existing few comprehensive review articles on H_(2)O_(2) production by two-electron oxygen reduction, the present review first explains the principle of the oxygen reduction reaction and then highlights recent advances in the regulation and control strategies of different types of catalysts. Key factors of electrode structure and device design are discussed. In addition,we highlight the promising co-production combination of this system with renewable energy or energy storage systems. This review can help introduce the potential of oxygen reduction electrochemical production of high-flux H_(2)O_(2) to the commercial market.
基金financially supported by the National Natural Science Foundation of China(No.21973028,52004334)the outstanding youth science fund of Henan Normal University(No.2021JQ02),Natural Science Foundation of Hunan Province(2021JJ20073)+2 种基金National Key Research and Development Program of China(2018YFC1901601 and 2019YFC1907801)Scientific Research Fund of Hunan Provincial Education Department,grant number(20C0085)Collaborative Innovation Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources,Foundation of State Key Laboratory of Mineral Processing(BGRIMM-KJSKL-2017-13)。
文摘Attracted by high energy density and considerable conductivity of selenium(Se),Na-Se batteries have been deemed promising energy-storage systems.But,it still suffers from sluggish kinetic behaviors and similar“shuttling effect”to S-electrodes.Herein,utilizing uniform hollow carbon spheres as precursors,Se-material is effectively loaded through vapor-infiltration method.Owing to the distribution of optimized pores,the content of microspores could be up to~60%(<2 nm),serving important roles for the physical confinement effect.Meanwhile,the rich oxygen-containing groups and N-elements could be noted,inducing the evolution of electron-moving behaviors.More significantly,assisted by the interfacial C-Se bonds and tiny Se distributions,Se electrodes are activated during cycling.Used as cathodes for Na-Se systems,the as-resulted samples display a capacity of 593.9 mA h g^(-1)after 100 cycles at the current density of 0.1 C.Even after 6000 cycles,the capacity could be still kept at about 225 mA h g^(-1)at 5.0 C.Supported by the detailed kinetic analysis,the designed microspores size induces the increasing redox reaction of nano Se,whilst the surface traits further render the enhancement of pseudo-capacitive contributions.Moreover,after cycling,the product Sex(x<4)in pores serves as the primary active material.Given this,the work is anticipated to provide an effective strategy for advanced electrodes for Na-Se systems.
基金supported by the National Natural Science Foundation of China(Grant Nos.12025503,U1867215,and U1932134)Hubei Provincial Natural Science Foundation(Grant No.2019CFA036)+1 种基金the Fundamental Research Funds for the Central Universities,China(Grant No.2042020kf0211)China Postdoctoral Science Foundation(Grant No.2020M682429)。
文摘Introducing heteroatoms and defects is a significant strategy to improve oxygen evolution reaction(OER)performance of electrocatalysts.However,the synergistic interaction of the heteroatom and defect still needs further investigations.Herein,we demonstrated an oxygen vacancy-rich vanadium-doped Co_(3)O_(4)(V-Ov-Co_(3)O_(4)),fabricated by V-ion implantation,could be used for high-efficient OER catalysis.X-ray photoelectron spectra(XPS)and density functional theory(DFT)calculations show that the charge density of Co atom increased,and the reaction barrier of reaction pathway from O∗to HOO∗decreased.V-Ov-Co_(3)O_(4) catalyst shows a low overpotential of 329 mV to maintain current density of 10 mA·cm^(−2),and a small Tafel slope of 74.5 mV·dec^(−1).This modification provides us with valuable perception for future design of heteroatom-doped and defect-based electrocatalysts.
基金the National Natural Science Foundation of China(Grant Nos.51772089,21872046 and 51902100)the Outstanding Youth Scientist Foundation of Hunan Province(Grant No.2018JJ1009)+5 种基金the Youth 1000 Talent Program of Chinathe Science and Technology Innovation Platform and Talent Plan of Hunan Province(Grant No.2017XK2023)the Research and Development Plan of Key Areas in Hunan Province(Grant No.2019GK2235)China Postdoctoral Science Foundation(2018M642971)the Youth Scientist Foundation of Hunan Province(Grant No.2019JJ50087)the Shenzhen Science and Technology Innovation Committee(Grant No.JCYJ20151013162733704)。
文摘Highly efficient electrocatalysts towards hydrogen evolution reaction(HER) with large current density at all-pH values are critical for the sustainable hydrogen production. Herein, we report a free-standing HER electrode, phosphorous-doped molybdenum nitride nanoparticles embedded in 3-dimentional carbon nanosheet matrix(P-Mo2N-CNS) fabricated via one-step carbonization and in-situ formation. The asprepared catalyst shows free-standing architecture with interconnected porous microstructure. P-doped Mo2N nanoparticles with an average diameter of 4.4 nm are well embedded in the 3-dimentional vertical carbon nanosheets matrix. Remarkable electrocatalytic HER performance is observed in alkaline, neutral and acidic media at large current densities. The overpotential of P-Mo2N-CNS to drive a current density of 100 mA cm-2 in 0.5 M H2SO4 and 1.0 M PBS is only 181 and 221 mV, respectively. In particular, the current density reaches up to 1000 mA cm-2 at a low overpotential of 256 mV in 1.0 M KOH, much better than that of the commercial Pt/C catalyst. Density functional theory calculations suggest the optimized H sorption kinetics on Mo2N after P doping, elucidating the superior activity.
基金financially supported by the National Natural Science Foundation of China-Yunnan Joint Fund(U2002213)Science and Technology Talent and Platform Program of Yunnan Provincial Science and Technology Department(202305AM070001)+1 种基金the Xingdian Talent Program of Yunnan Provincethe Double-First Class University Plan(C176220100042).
文摘The recycling of CO_(2)through electrochemical processes offers a promising solution for alleviating the greenhouse effect;however,the activation of CO_(2)and desorption of^(*)CO in electrocatalytic CO_(2)reduction(ECR)frequently encounter high energy barriers and competitive hydrogen evolution reactions(HERs),which are urgent problems that need to be addressed.In this study,a catalyst(P100-Fe-N/C)with homogeneous P-tuned FeN_(2)binuclear sites(N_(2)PFe-FePN_(2))was successfully synthesised,demonstrating satisfactory performance in the ECR to CO.P100-Fe-N/C attains a peak FECOof 98.01%and a normalized TOF of 664.7 h-1at-0.7 VRHE,surpassing the performance of the Fe binuclear catalyst without P and singleatoms catalysts.In the MEA cell,a FECOexceeding 90%can still be achieved.Density functional theory analysis indicates that the asymmetric coordination configuration induced by the incorporation of P facilitates a reduction in the system's energy.The modulation of P results in the d-band centre of the catalyst being positioned closer to the Fermi level,which facilitates the interaction of the catalyst with CO_(2),allowing more electrons to be injected into the CO_(2)molecule at the Fe binuclear sites and inhibiting the HER.The P-tuned FeN_(2)binuclear sites effectively lower the^(*)CO desorption barrier.
