Single atom catalysts(SACs)have attracted considerable attention due to their unique structures and excellent catalytic performance,especially in the area of catalysis science and energy conversion and storage.In rece...Single atom catalysts(SACs)have attracted considerable attention due to their unique structures and excellent catalytic performance,especially in the area of catalysis science and energy conversion and storage.In recent years,SACs have emerged as a new type of sensing material for constructing electrochemical sensors(ECSs),presenting excellent sensitivity,selectivity,and stability.Herein,we review the recent advances of SACs in electrochemical sensing and discuss the status quo of current SAC-based ECSs.Specifically,the fundamentals of SAC-based ECSs are outlined,including the involved central metal atoms and various supports of SACs in this field,the detection mechanisms,and improving strategies of SAC-based ECSs.Moreover,the important applications of SAC-based ECSs are listed and classified,covering the detection of reactive oxygen and nitrogen species,environmental pollutants,disease biomarkers,and pharmaceuticals.Last,based on abundant reported cases,the current conundrums of SAC-based ECSs are summarized,and the prediction of their future developing trends is also put forward.展开更多
The development of highly efficient and costeffective oxygen evolution reaction(OER)electrocatalysts for renewable energy systems is vitally essential.Modulation of the electronic structure through heteroatom doping i...The development of highly efficient and costeffective oxygen evolution reaction(OER)electrocatalysts for renewable energy systems is vitally essential.Modulation of the electronic structure through heteroatom doping is considered as one of the most potential strategies to boost OER performances.Herein,a rational design of Mn-doped NiFe layered double hydroxide/reduced graphene oxide(Mn-NiFe LDH/rGO)is demonstrated by a facile hydrothermal approach,which exhibits outstanding OER activity and durability.Experimental results and density functional theory(DFT)calculations manifest that the introduction of Mn can reprogram the electronic structure of surface active sites and alter the intermediate adsorption energy,consequently reducing the potential limiting activation energy for OER.Specifically,the optimal Mn-NiFe LDH/rGO composite shows an enhanced OER performance with an ultralow overpotential of 240 mV@10 mA cm^(-2),Tafel slope of 40.0 mV dec^(-1) and excellent stability.Such superior OER activity is comparable to those of the recently reported state-of-the-art OER catalysts.This work presents an advanced strategy for designing electrocatalysts with high activity and low cost for energy conversion applications.展开更多
In recent years,the isolated single-atom site(ISAS)catalysts have attracted much attention as they are cost-effective,can achieve 100%atom-utilization efficiency,and often display superior catalytic performance.Here,w...In recent years,the isolated single-atom site(ISAS)catalysts have attracted much attention as they are cost-effective,can achieve 100%atom-utilization efficiency,and often display superior catalytic performance.Here,we developed a biomass-assisted pyrolysis-etching-activation(PEA)strategy to construct ISAS metal decorated on N and B co-doped porous carbon(ISAS M/NBPC,M=Co,Fe,or Ni)catalysts.This PEA strategy can be applied in the universal and large-scale preparation of ISAS catalysts.Interestingly,the ISAS M/NBPC(M=Co,Fe,or Ni)catalysts show multi-functional features and excellent catalytic activities.They can be used to conduct different types of catalytic reactions,such as O-silylation(OSI),oxidative dehydrogenation(ODH),and transfer hydrogenation(THG).In addition,we used the transfer hydrogenation of nitrobenzene as a typical reaction and revealed the difference between ISAS Co/NBPC and ISAS Co/NPC(N-doped porous carbon)catalysts by density functional theory(DFT)calculations,and which showed that the decreased barrier of the ratedetermining step and the low-lying potential energy diagram indicate that the catalytic activity is higher when ISAS Co/NBPC is used than that when ISAS Co/NPC is used.These results demonstrate that the catalytic performance can be effectively improved by adjusting the coordination environment around the ISAS.展开更多
Self-assembled Fe_(3)O_(4)hierarchical microspheres(HMSs) were prepared by a one-pot synchronous reduction–self-assembling (SRSA) hydrothermal method.In this simple and inexpensive synthetic process,only glycerol,wat...Self-assembled Fe_(3)O_(4)hierarchical microspheres(HMSs) were prepared by a one-pot synchronous reduction–self-assembling (SRSA) hydrothermal method.In this simple and inexpensive synthetic process,only glycerol,water,and a single iron source (potassium ferricyanide (K3[Fe(CN)6]))were employed as reactants without additional reductants,surfactants,or additives.The iron source,K3[Fe(CN)6],and glycerol significantly affected the synthesis of Fe_(3)O_(4)HMSs.Fe_(3)O_(4)HMSs with a self-assembled spherical shape readily functioned as high-performance anode materials for lithiumion batteries with a specific capacity of>1000 mA h g^(-1)at0.5 A g^(-1)after 270 cycles.Further charging and discharging results revealed that Fe_(3)O_(4)HMSs displayed good reversible performance (>1000 mA h g^(-1)) and cycling stability (700 cycles) at 0.5 A g^(-1).Furthermore,as multifunctional materials,the as-obtained Fe_(3)O_(4)HMSs also exhibited high saturation magnetization (99.5 emu g^(-1)) at room temperature (25°C) and could be further employed as efficient and magnetically recyclable catalysts for the hydrogenation of nitro compounds.展开更多
In the field of electrolysis of water,the design and synthesis of catalysts over a wide pH range have attracted extensive attentions.In this paper,Co and N are co-introduced into the structural unit of tungsten disulf...In the field of electrolysis of water,the design and synthesis of catalysts over a wide pH range have attracted extensive attentions.In this paper,Co and N are co-introduced into the structural unit of tungsten disulfide(WS_(2)),and the hydrogen evolution reaction(HER)performances of different WS_(2)-based catalysts are theoretically predicted and systematically studied by density functional theory(DFT)calculations.With the guidance of DFT calculations,an evaporation-pyrolysis strategy is applied to prepare Co and N co-doped WS_(2)(Co,N-WS_(2))flower-like nanosheets,which exhibits excellent HER performance over a wide pH range.In addition,the DFT calculations show that the active sites in Co,N-WS_(2) have a good ability of hydrogen adsorption after the introduction of Co and N,suggesting that such a co-doping system will be an ideal catalyst for oxidative dehydrogenation(ODH).The following experiment results indeed evidence that the Co,N-WS_(2) catalyst displays a high activity in the ODH of 1,2,3,4-tetrahydroquinoline(4H-quinoline)and its derivatives.Therefore,this work provides a good example for the rational design and accurate preparation of functional catalysts,which enables it possible to develop other efficient catalysts with multiple functions.展开更多
Dual-active sites(DASs)catalysts have positive potential applications in broad fields because of their specific active sites and synergistic catalytic effects.Therefore,the controllable synthesis and finely regulating...Dual-active sites(DASs)catalysts have positive potential applications in broad fields because of their specific active sites and synergistic catalytic effects.Therefore,the controllable synthesis and finely regulating the activity of such catalysts has become a hot research area for now.In this work,we developed a pyrolysis-etching-hydrogen activation strategy to prepare the DASs catalysts involving single-atom Cu and B on N-doped porous carbon material(Cu_(1)-B/NPC).Numerous systematic characterization and density functional theoretical(DFT)calculation results showed that the Cu and B existed as Cu-N4 porphyrinlike unit and B-N_(3)unit in the obtained catalyst.DFT calculations further revealed that single-atom Cu and B sites were linked by bridging N atoms to form the Cu_(1)-B-N6 dual-sites.The Cu_(1)-B/NPC catalyst was more effective than the single-active site catalysts with B-N_(3)sites in NPC(B/NPC)and Cu-N4 porphyrin-like sites in NPC(Cu_(1)/NPC),respectively,for the dehydrogenative coupling of dimethylphenylsilane(DiMPSH)with various alcohols,performing the great activity(>99%)and selectivity(>99%).The catalytic performances of the Cu_(1)-B/NPC catalyst remained nearly unchanged after five cycles,also indicating its outstanding recyclability.DFT calculations showed that the Cu_(1)-B-N6 dual-sites exhibited the lowest energy profile on the potential energy surface than that of sole B-N_(3)and Cu-N4 porphyrin-like sites.Furthermore,the rate-limiting step of dehydrogenation of DiMPSH on Cu_(1)-B-N6 dual-sites also showed a much lower activation energy than the other two single sites.Benefitting from the superiority of the Cu_(1)-B-N6 dual-sites,the Cu_(1)-B/NPC catalyst can also be used for CO_(2)electroreduction to produce syngas.Thus,DASs catalysts are promising to achieve multifunctional catalytic properties and have aroused positive attention in the field of catalysis.展开更多
Highly efficient hydrogen evolution reaction(HER)electrocatalysts play a crucial part in generating green hydrogen.Herein,an electrochemical activation approach was applied to design 6.7 Rh-Ni_(2)P-800CV electrocataly...Highly efficient hydrogen evolution reaction(HER)electrocatalysts play a crucial part in generating green hydrogen.Herein,an electrochemical activation approach was applied to design 6.7 Rh-Ni_(2)P-800CV electrocatalysts in alkaline electrolytes.The results confirm that the generation of metal oxide sites through the electrochemical activation strategy can effectively improve the intrinsic activity of 6.7 Rh-Ni_(2)P-800CV.The density functional calculations further confirm that metal oxide active sites are favorable for H2O adsorption and activation and H*adsorption/desorption.The 6.7 Rh-Ni_(2)P-800CV possesses significantly enhanced HER performance with low overpotential(25 mV at 10 mA·cm^(2)),small Tafel(60 mV·dec^(-1))and robust stability in 1.0 M KOH,outperforming Pt/C and 6.7 Rh-Ni_(2)P counterparts.Meanwhile,6.7 Rh-Ni_(2)P-800CV can even operate at a large current density(550 mA·cm^(-2))up to 90 h with an overpotential of 320 mV,which meets the requirements of industrial water splitting.What's more,the overall watersplitting systems(6.7 Rh-Ni_(2)P-800CV‖6.7 Rh-Ni_(2)P-800CV)can be directly driven by the solar cell.This work highlights that electrochemical activation technology provides a robust avenue toward constructing efficient electrocatalysts for sustainable energy conversion.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22375005 and 21771003)the Natural Science Research Project of Anhui Province Education Department(Nos.2022AH050323 and 2023AH051116)+1 种基金the Major industrial innovation plan of Anhui Province(No.AHZDCYCX-LSDT2023-04)the University Synergy Innovation Program of Anhui Province(No.GXXT-2022-006).
文摘Single atom catalysts(SACs)have attracted considerable attention due to their unique structures and excellent catalytic performance,especially in the area of catalysis science and energy conversion and storage.In recent years,SACs have emerged as a new type of sensing material for constructing electrochemical sensors(ECSs),presenting excellent sensitivity,selectivity,and stability.Herein,we review the recent advances of SACs in electrochemical sensing and discuss the status quo of current SAC-based ECSs.Specifically,the fundamentals of SAC-based ECSs are outlined,including the involved central metal atoms and various supports of SACs in this field,the detection mechanisms,and improving strategies of SAC-based ECSs.Moreover,the important applications of SAC-based ECSs are listed and classified,covering the detection of reactive oxygen and nitrogen species,environmental pollutants,disease biomarkers,and pharmaceuticals.Last,based on abundant reported cases,the current conundrums of SAC-based ECSs are summarized,and the prediction of their future developing trends is also put forward.
基金the National Natural Science Foundation of China(51902003 and 21771003)Anhui Province Natural Science Foundation(2008085QB53)the Natural Science Research Project of Anhui Province Education Department(KJ2019A0581)。
文摘The development of highly efficient and costeffective oxygen evolution reaction(OER)electrocatalysts for renewable energy systems is vitally essential.Modulation of the electronic structure through heteroatom doping is considered as one of the most potential strategies to boost OER performances.Herein,a rational design of Mn-doped NiFe layered double hydroxide/reduced graphene oxide(Mn-NiFe LDH/rGO)is demonstrated by a facile hydrothermal approach,which exhibits outstanding OER activity and durability.Experimental results and density functional theory(DFT)calculations manifest that the introduction of Mn can reprogram the electronic structure of surface active sites and alter the intermediate adsorption energy,consequently reducing the potential limiting activation energy for OER.Specifically,the optimal Mn-NiFe LDH/rGO composite shows an enhanced OER performance with an ultralow overpotential of 240 mV@10 mA cm^(-2),Tafel slope of 40.0 mV dec^(-1) and excellent stability.Such superior OER activity is comparable to those of the recently reported state-of-the-art OER catalysts.This work presents an advanced strategy for designing electrocatalysts with high activity and low cost for energy conversion applications.
基金This work was supported by the National Natural Science Foundation of China(Nos.21771003,51902003,21901007,22002085,and 21501004)the University Synergy Innovation Program of Anhui Province(No.GXXT-2021-020)+3 种基金the Anhui Province Natural Science Foundation(Nos.2008085QB53 and 2008085QB83)the Natural Science Research Project of Anhui Province Education Department(No.KJ2019A0581)the Open Project of Key Laboratory of Metallurgical Emission Reduction&Resources Recycling of Ministry of Education(No.JKF21-03)the Open Foundation of Anhui Laboratory of Clean Catalytic Engineering(No.LCCE-01).
文摘In recent years,the isolated single-atom site(ISAS)catalysts have attracted much attention as they are cost-effective,can achieve 100%atom-utilization efficiency,and often display superior catalytic performance.Here,we developed a biomass-assisted pyrolysis-etching-activation(PEA)strategy to construct ISAS metal decorated on N and B co-doped porous carbon(ISAS M/NBPC,M=Co,Fe,or Ni)catalysts.This PEA strategy can be applied in the universal and large-scale preparation of ISAS catalysts.Interestingly,the ISAS M/NBPC(M=Co,Fe,or Ni)catalysts show multi-functional features and excellent catalytic activities.They can be used to conduct different types of catalytic reactions,such as O-silylation(OSI),oxidative dehydrogenation(ODH),and transfer hydrogenation(THG).In addition,we used the transfer hydrogenation of nitrobenzene as a typical reaction and revealed the difference between ISAS Co/NBPC and ISAS Co/NPC(N-doped porous carbon)catalysts by density functional theory(DFT)calculations,and which showed that the decreased barrier of the ratedetermining step and the low-lying potential energy diagram indicate that the catalytic activity is higher when ISAS Co/NBPC is used than that when ISAS Co/NPC is used.These results demonstrate that the catalytic performance can be effectively improved by adjusting the coordination environment around the ISAS.
基金the financial support from the National Natural Science Foundation of China (21501004,21771003,21901007 and 21671005)Anhui Provincial Natural Science Foundation for Distinguished Youth (1808085J27)。
文摘Self-assembled Fe_(3)O_(4)hierarchical microspheres(HMSs) were prepared by a one-pot synchronous reduction–self-assembling (SRSA) hydrothermal method.In this simple and inexpensive synthetic process,only glycerol,water,and a single iron source (potassium ferricyanide (K3[Fe(CN)6]))were employed as reactants without additional reductants,surfactants,or additives.The iron source,K3[Fe(CN)6],and glycerol significantly affected the synthesis of Fe_(3)O_(4)HMSs.Fe_(3)O_(4)HMSs with a self-assembled spherical shape readily functioned as high-performance anode materials for lithiumion batteries with a specific capacity of>1000 mA h g^(-1)at0.5 A g^(-1)after 270 cycles.Further charging and discharging results revealed that Fe_(3)O_(4)HMSs displayed good reversible performance (>1000 mA h g^(-1)) and cycling stability (700 cycles) at 0.5 A g^(-1).Furthermore,as multifunctional materials,the as-obtained Fe_(3)O_(4)HMSs also exhibited high saturation magnetization (99.5 emu g^(-1)) at room temperature (25°C) and could be further employed as efficient and magnetically recyclable catalysts for the hydrogenation of nitro compounds.
基金the National Natural Science Foundation of China(Nos.21771003,51902003,and 21501004)the University Synergy Innovation Program of Anhui Province(No.GXXT-2021-020)+1 种基金the Natural Science Foundation of Anhui Province(No.2008085QB53)the Natural Science Research Project of Anhui Province Education Department(No.KJ2019A0581).
文摘In the field of electrolysis of water,the design and synthesis of catalysts over a wide pH range have attracted extensive attentions.In this paper,Co and N are co-introduced into the structural unit of tungsten disulfide(WS_(2)),and the hydrogen evolution reaction(HER)performances of different WS_(2)-based catalysts are theoretically predicted and systematically studied by density functional theory(DFT)calculations.With the guidance of DFT calculations,an evaporation-pyrolysis strategy is applied to prepare Co and N co-doped WS_(2)(Co,N-WS_(2))flower-like nanosheets,which exhibits excellent HER performance over a wide pH range.In addition,the DFT calculations show that the active sites in Co,N-WS_(2) have a good ability of hydrogen adsorption after the introduction of Co and N,suggesting that such a co-doping system will be an ideal catalyst for oxidative dehydrogenation(ODH).The following experiment results indeed evidence that the Co,N-WS_(2) catalyst displays a high activity in the ODH of 1,2,3,4-tetrahydroquinoline(4H-quinoline)and its derivatives.Therefore,this work provides a good example for the rational design and accurate preparation of functional catalysts,which enables it possible to develop other efficient catalysts with multiple functions.
基金supported by the National Natural Science Foundation of China(Nos.51902003,22002085,21771003,21501004)the University Synergy Innovation Program of Anhui Province(No.GXXT-2021-020)+4 种基金the Anhui Province Natural Science Foundation(Nos.2108085QB71 and 2008085QB53)the Natural Science Research Project of Anhui Province Education Department(No.KJ2019A0581)the Open Project of Key Laboratory of Metallurgical Emission Reduction&Resources Recycling of Ministry of Education(No.JKF21-03)the Open Foundation of Anhui Laboratory of Clean Catalytic Engineering(No.LCCE-01)the Open Research Funds of Jiangxi Province Engineering Research Center of Ecological Chemical Industry(STKF2109).
文摘Dual-active sites(DASs)catalysts have positive potential applications in broad fields because of their specific active sites and synergistic catalytic effects.Therefore,the controllable synthesis and finely regulating the activity of such catalysts has become a hot research area for now.In this work,we developed a pyrolysis-etching-hydrogen activation strategy to prepare the DASs catalysts involving single-atom Cu and B on N-doped porous carbon material(Cu_(1)-B/NPC).Numerous systematic characterization and density functional theoretical(DFT)calculation results showed that the Cu and B existed as Cu-N4 porphyrinlike unit and B-N_(3)unit in the obtained catalyst.DFT calculations further revealed that single-atom Cu and B sites were linked by bridging N atoms to form the Cu_(1)-B-N6 dual-sites.The Cu_(1)-B/NPC catalyst was more effective than the single-active site catalysts with B-N_(3)sites in NPC(B/NPC)and Cu-N4 porphyrin-like sites in NPC(Cu_(1)/NPC),respectively,for the dehydrogenative coupling of dimethylphenylsilane(DiMPSH)with various alcohols,performing the great activity(>99%)and selectivity(>99%).The catalytic performances of the Cu_(1)-B/NPC catalyst remained nearly unchanged after five cycles,also indicating its outstanding recyclability.DFT calculations showed that the Cu_(1)-B-N6 dual-sites exhibited the lowest energy profile on the potential energy surface than that of sole B-N_(3)and Cu-N4 porphyrin-like sites.Furthermore,the rate-limiting step of dehydrogenation of DiMPSH on Cu_(1)-B-N6 dual-sites also showed a much lower activation energy than the other two single sites.Benefitting from the superiority of the Cu_(1)-B-N6 dual-sites,the Cu_(1)-B/NPC catalyst can also be used for CO_(2)electroreduction to produce syngas.Thus,DASs catalysts are promising to achieve multifunctional catalytic properties and have aroused positive attention in the field of catalysis.
基金financially supported by the National Natural Science Foundation of China(Nos.22375005,22103054 and 22173066)the Natural Science Research Project of Anhui Province Education Department(No.2022AH050323)+3 种基金the Foundation of Key Laboratory of Advanced Technique&Preparation for Renewable Energy Materials,Ministry of Education,Yunnan Normal University(No.OF2022-05)partly supported by Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectJoint International Research Laboratory of Carbon-Based Functional Materials and Devices。
文摘Highly efficient hydrogen evolution reaction(HER)electrocatalysts play a crucial part in generating green hydrogen.Herein,an electrochemical activation approach was applied to design 6.7 Rh-Ni_(2)P-800CV electrocatalysts in alkaline electrolytes.The results confirm that the generation of metal oxide sites through the electrochemical activation strategy can effectively improve the intrinsic activity of 6.7 Rh-Ni_(2)P-800CV.The density functional calculations further confirm that metal oxide active sites are favorable for H2O adsorption and activation and H*adsorption/desorption.The 6.7 Rh-Ni_(2)P-800CV possesses significantly enhanced HER performance with low overpotential(25 mV at 10 mA·cm^(2)),small Tafel(60 mV·dec^(-1))and robust stability in 1.0 M KOH,outperforming Pt/C and 6.7 Rh-Ni_(2)P counterparts.Meanwhile,6.7 Rh-Ni_(2)P-800CV can even operate at a large current density(550 mA·cm^(-2))up to 90 h with an overpotential of 320 mV,which meets the requirements of industrial water splitting.What's more,the overall watersplitting systems(6.7 Rh-Ni_(2)P-800CV‖6.7 Rh-Ni_(2)P-800CV)can be directly driven by the solar cell.This work highlights that electrochemical activation technology provides a robust avenue toward constructing efficient electrocatalysts for sustainable energy conversion.
