The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of...The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of electrocatalysts to optimize the catalytic activity and ammonia selectivity.Herein,the Cu-based catalysts were tailored at the atomic level to exhibit a size gradient ranging from single-atom catalysts(SACs,0.15–0.35 nm)to single-cluster catalysts(SCCs,1.0–2.8 nm)and nanoparticles(NPs,20–30 nm),with the aim of studying the size effect for the NO_(3)^(-)-to-NH_(3) reduction reaction.Especially,the Cu SCCs exhibit enhanced metal–substrate and metal–metal interactions by taking advantageous features of Cu SACs and Cu NPs.Thus,Cu SCCs achieve exceptional electrocatalytic performance for the NitRR with a maximum Faradaic efficiency of ca.96%NH_(3)and the largest yield rate of ca.1.99 mg·h^(-1)·cm^(-2) at-0.5 V vs.reversible hydrogen electrode(RHE).The theoretical calculation further reveals the size effect and coordination environment on the high catalytic activity and selectivity for the NitRR.This work provides a promising various size-controlled design strategy for aerogel-based catalysts effectively applied in various electrocatalytic reactions.展开更多
Metallic clusters,ranging from 1 to 2 nm in size,have emerged as promising candidates for creating nanoelectronic devices at the single-cluster level.With the intermediate quantum properties between metals and semicon...Metallic clusters,ranging from 1 to 2 nm in size,have emerged as promising candidates for creating nanoelectronic devices at the single-cluster level.With the intermediate quantum properties between metals and semiconductors,these metallic clusters offer an alternative pathway to silicon-based electronics and organic molecules for miniaturized electronics with dimensions below 5 nm.Significant progress has been made in studies of single-cluster electronic devices.However,a clear guide for selecting,synthesizing,and fabricating functional single-cluster electronic devices is still required.This review article provides a comprehensive overview of single-cluster electronic devices,including the mechanisms of electron transport,the fabrication of devices,and the regulations of electron transport properties.Furthermore,we discuss the challenges and future directions for single-cluster electronic devices and their potential applications.展开更多
While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts...While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts(SCCs)a natural extension in the domain of heterogeneous catalysis.SCCs with precise numbers of atoms and structural configurations possess SAC merits,yet have greater potential for catalyzing complex reactions and/or bulky reactants.Through systematic quantum-chemical studies and computational screening,we report here the rational design of transition metal three-atom clusters anchored on graphdiyne(GDY)as a novel kind of stable SCC with great promise for efficient and atomically precise heterogenous catalysis.By investigating their structure and catalytic performance for the oxygen reduction reaction,the hydrogen evolution reaction,and the CO_(2)reduction reaction,we have provided theoretical guidelines for their potential applications as heterogeneous catalysts.These GDY-supported three-atom SCCs provide an ideal benchmark scaffold for rational design of atomically precise heterogeneous catalysts for industrially important chemical reactions.展开更多
Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,...Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,the catalytic activities of transition metal clusters with precise numbers of atoms supported on graphdiyne(TM_(1-4)@GDY,TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Pd,Ir,Pt) were investigated for oxygen evolution reactions(OER),oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER).The computed results reveal that the Pd_(2),Pd_(4) and Pt_(1) anchored graphdiyne can serve as trifunctional catalysts for OER/ORR/HER with the overpotentials of 0.49/0.37/0.06,0.45/0.33/0.12 and 0.37/0.43/0.01 V,respectively,while Pd_(1) and Pt_(2)@graphdiyne can exhibit excellent catalytic performance for water splitting(OER/HER) with the overpotentials of 0.55/0.17 and 0.43/0.03 V.In addition,Ni_(1) and Pd_(3) anchored GDY can perform as bifunctional catalysts for metal-air cells(OER/ORR) and fuels cells(ORR/HER) with the overpotentials of 0.34/0.32 and 0.42/0.04 V,respectively.Thus,by precisely controlling the numbers of atoms in clusters,the TM_(1-4) anchored graphdiyne can serve as promising multifunctional electrocatalysts for OER/ORR/HER,which may provide an instructive strategy to design catalysts for the energy conversation and storage devices.展开更多
Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challengin...Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challenging mainly due to the coverage of bulky ligands on the noble clusters.Using the scanning tunneling microscopy break junction(STM-BJ)technique,we have developed a“direct contact”approach to fabrication and investigation of the charge transport through single-cluster junctions of AgCu bimetallic metal clusterswith different halide anchors.Wefound that the electrodes could make contact directly with the surface halides of the single-cluster junctions and experience different contact resistance from different halogen atoms.Experiments and calculations reveal that the halide anchors provided efficient coupling between the cluster and the electrode,and the enhanced coupling with various halide anchors promoted electron transport and improved transmission probability.Our work offers a“direct contact”strategy for interface design between clusters of noble metals and electrodes,an essential step in progress toward single-cluster electronics.展开更多
Single cluster catalysts(SCCs),which exhibit remarkable catalytic performance due to their high metal loading and synergy effect between metal atoms,have attracted great attention in research.Herein,by means of densit...Single cluster catalysts(SCCs),which exhibit remarkable catalytic performance due to their high metal loading and synergy effect between metal atoms,have attracted great attention in research.Herein,by means of density functional theory calculations,the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER)performances of precious metal(Pt,Pd,Rh,Ir)trimetallic single-cluster electrocatalyst(U_(x)V_(y)W_(z)-NG)are investigated.The calculation results show that Pt,Pd,Ir have significant effect on ORR,OER,HER,respectively,all the calculated U_(x)V_(y)W_(z)-NG structures are thermodynamically stable due to the negative formation energies and binding energies.The Pt_(3)-NG,Pd_(3)-NG,Ir_(3)-NG show the lowest ORR,OER,HER overpotentials of 0.63,0.77,−0.02 V,respectively,among all combinations of U_(x)V_(y)W_(z)-NG.These overpotentials are lower than that of precious metal single atom catalysts(SACs),which indicate better activities of precious trimetallic SCCs than those of SACs.The electronic structure reveals that the O-2p orbital shows strong hybridization strength with Pt-3d orbitals in the system of OH adsorbed Pt_(3)-NG and thus facilitates the electrocatalytic reactions.The results are helpful for the rational design of high-performance triatomic catalysts.展开更多
Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experim...Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experimental and theoretical advances on single-cluster catalysts(SCCs),we systematically investigated the catalytic performance of various triple-transition-metal-atom clusters anchored on nitrogen-doped graphene for NRR through density functional theory(DFT)calculation.Among them,Mn_(3)-N4,Fe_(3)-N4,Co_(3)-N4,and Mo_(3)-N4 were screened out as electrocatalysis systems composed of non-noble metal with high activity,selectivity,stability,and feasibility.Particularly,the Co_(3)-N4 possesses the highest activity with a limiting potential of-0.41 V through the enzymatic mechanism.The outstanding performance of Co_(3)-N4 can be attributed to the unique electronic structure leading to strong π backdonation,which is crucial in effective N_(2) activation.This work not only predicts four efficient non-noble metal electrocatalysts for NRR,but also suggest the SCCs can serve as potential candidates for other important electrochemical reactions.展开更多
Confined metal clusters as sub-nanometer reactors for electrocatalytic N_(2) reduction reaction(eNRR)have received increasing attention due to the unique metal-metal interaction and higher activity than singleatom cat...Confined metal clusters as sub-nanometer reactors for electrocatalytic N_(2) reduction reaction(eNRR)have received increasing attention due to the unique metal-metal interaction and higher activity than singleatom catalysts.Herein,the inspiration of the superior capacitance and unique microenvironment with regular surface cavities of the porous boron nitride(p-BN)nanosheets,we systematically studied the catalytic activity for NRR of transition-metal single-clusters in the triplet form(V_(3),Fe_(3),Mo_(3) and W_(3))confined in the surface cavities of the p-BN sheets by spin-polarized density functional theory(DFT)calculations.After a two-step screening strategy,Mo_(3)@p-BN was found to have high catalytic activity and selectivity with a rather low limiting potential(-0.34 V)for the NRR.The anchored Mo_(3) singlecluster can be stably embedded on the surface cavities of the substrate preventing the diffusion of the active Mo atoms.More importantly,the Mo atoms in the Mo_(3) single-cluster would act as“cache”to accelerate electron transfer between active metal centers and nitrogen-containing intermediates via the intimate Mo-Mo interactions.The cooperation of Mo atoms can also provide a large number of occupied and unoccupied d orbitals to make the"donation-backdonation"mechanism more effective.This work not only provides a quite promising electrocatalyst for NRR,but also brings new insights into the rational design of triple-atom NRR catalysts.展开更多
A novel (Me 3PhCH 2N) 2[MoFe 4S 4(SC 6H 11 ) 7] cubane like cluster was obtained from a reaction system including (NH 4) 2MoS 4, FeCl 2 and NaSC 6H 11 in methanol, and characterized by X ray crystallography. The title...A novel (Me 3PhCH 2N) 2[MoFe 4S 4(SC 6H 11 ) 7] cubane like cluster was obtained from a reaction system including (NH 4) 2MoS 4, FeCl 2 and NaSC 6H 11 in methanol, and characterized by X ray crystallography. The title compound crystallizes in triclinic space group P 1 with a =1.523 1(3), b =1.610 5(3), c =1.838 3(4) nm, α =77.18 (3)°, β =75.17(3)°, γ =64.60 (3)°, and Z =2. Also included in this paper are the discussions on the variation of the reaction products obtained from the participation of cyclohexylthiolate and on the changes of the structural features of the products.展开更多
基金support from the National Nature Science Foundation of China(No.52202372)the Sichuan Science and Technology Program(Nos.2023NSFSC0436 and 2023NSFSC0089)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.YJ2021151 and 20826041G4185)T.T.G.acknowledges the Chengdu University new faculty start-up funding(No.2081920074).
文摘The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of electrocatalysts to optimize the catalytic activity and ammonia selectivity.Herein,the Cu-based catalysts were tailored at the atomic level to exhibit a size gradient ranging from single-atom catalysts(SACs,0.15–0.35 nm)to single-cluster catalysts(SCCs,1.0–2.8 nm)and nanoparticles(NPs,20–30 nm),with the aim of studying the size effect for the NO_(3)^(-)-to-NH_(3) reduction reaction.Especially,the Cu SCCs exhibit enhanced metal–substrate and metal–metal interactions by taking advantageous features of Cu SACs and Cu NPs.Thus,Cu SCCs achieve exceptional electrocatalytic performance for the NitRR with a maximum Faradaic efficiency of ca.96%NH_(3)and the largest yield rate of ca.1.99 mg·h^(-1)·cm^(-2) at-0.5 V vs.reversible hydrogen electrode(RHE).The theoretical calculation further reveals the size effect and coordination environment on the high catalytic activity and selectivity for the NitRR.This work provides a promising various size-controlled design strategy for aerogel-based catalysts effectively applied in various electrocatalytic reactions.
基金supported by the National Natural Science Foundation of China(Nos.22250003,22173075,21933012,and 22003052)the Fundamental Research Funds for the Central Universities(Nos.20720220020,20720220072,and 20720200068).
文摘Metallic clusters,ranging from 1 to 2 nm in size,have emerged as promising candidates for creating nanoelectronic devices at the single-cluster level.With the intermediate quantum properties between metals and semiconductors,these metallic clusters offer an alternative pathway to silicon-based electronics and organic molecules for miniaturized electronics with dimensions below 5 nm.Significant progress has been made in studies of single-cluster electronic devices.However,a clear guide for selecting,synthesizing,and fabricating functional single-cluster electronic devices is still required.This review article provides a comprehensive overview of single-cluster electronic devices,including the mechanisms of electron transport,the fabrication of devices,and the regulations of electron transport properties.Furthermore,we discuss the challenges and future directions for single-cluster electronic devices and their potential applications.
基金This work was financially supported by the National Natural Science Foundation of China(grant no.22033005 to J.L.and grant no.21903047 to H.X.)The support of Guangdong Provincial Key Laboratory of Catalysis(grant no.2020B121201002)is also acknowledged.The calculations were performed using the supercomputers at Tsinghua National Laboratory for Information Science and Technology,the Computational Chemistry Laboratory of the Department of Chemistry under the Tsinghua Xuetang Talents Program,and the Supercomputer Center of the Southern University of Science and Technology.
文摘While heterogeneous single-atom catalysts(SACs)have achieved great success in the past decade,their application is potentially limited by their simplistic single-atom active centers,which make single-cluster catalysts(SCCs)a natural extension in the domain of heterogeneous catalysis.SCCs with precise numbers of atoms and structural configurations possess SAC merits,yet have greater potential for catalyzing complex reactions and/or bulky reactants.Through systematic quantum-chemical studies and computational screening,we report here the rational design of transition metal three-atom clusters anchored on graphdiyne(GDY)as a novel kind of stable SCC with great promise for efficient and atomically precise heterogenous catalysis.By investigating their structure and catalytic performance for the oxygen reduction reaction,the hydrogen evolution reaction,and the CO_(2)reduction reaction,we have provided theoretical guidelines for their potential applications as heterogeneous catalysts.These GDY-supported three-atom SCCs provide an ideal benchmark scaffold for rational design of atomically precise heterogeneous catalysts for industrially important chemical reactions.
基金financially supported by Fundamental Research Funds for Heilongjiang Province universities (No.2021-KYYWF-0184)Harbin Normal University Graduate Student Innovation Project (No.HSDSSCX2023-30)。
文摘Subnanometer metal clusters play an increasingly important role in heterogeneous catalysis due to their high catalytic activity and selectivity.In this work,by means of the density functional theory(DFT) calculations,the catalytic activities of transition metal clusters with precise numbers of atoms supported on graphdiyne(TM_(1-4)@GDY,TM=V,Cr,Mn,Fe,Co,Ni,Cu,Ru,Rh,Pd,Ir,Pt) were investigated for oxygen evolution reactions(OER),oxygen reduction reactions(ORR) and hydrogen evolution reactions(HER).The computed results reveal that the Pd_(2),Pd_(4) and Pt_(1) anchored graphdiyne can serve as trifunctional catalysts for OER/ORR/HER with the overpotentials of 0.49/0.37/0.06,0.45/0.33/0.12 and 0.37/0.43/0.01 V,respectively,while Pd_(1) and Pt_(2)@graphdiyne can exhibit excellent catalytic performance for water splitting(OER/HER) with the overpotentials of 0.55/0.17 and 0.43/0.03 V.In addition,Ni_(1) and Pd_(3) anchored GDY can perform as bifunctional catalysts for metal-air cells(OER/ORR) and fuels cells(ORR/HER) with the overpotentials of 0.34/0.32 and 0.42/0.04 V,respectively.Thus,by precisely controlling the numbers of atoms in clusters,the TM_(1-4) anchored graphdiyne can serve as promising multifunctional electrocatalysts for OER/ORR/HER,which may provide an instructive strategy to design catalysts for the energy conversation and storage devices.
基金supported by the Foundation of Key Laboratory of Low-Carbon Conversion Science&Engineering,Shanghai Advanced Research Institute,Chinese Academy of Sciences(KLLCCSE201902,SARI,CAS)the National Natural Science Foundation of China(22033005,22002004,22273053 and 92261203)+3 种基金the National Key R&D Project(2022YFA1503900 and 2022YFA1503000)the NSFC Center for Single-Atom Catalysisthe Natural Science Basic Research Program of Shaanxi(S2020-JC-WT-0001 and S2021JCW-20)Support of Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)。
基金This work was supported by the National Key Research and Development Program of China(grant no.2017YFA0204902)the Fundamental Research Funds for Central Universities(grant no.20720180064)the Beijing National Laboratory for Molecular Sciences(grant no.BNLMS202005).
文摘Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challenging mainly due to the coverage of bulky ligands on the noble clusters.Using the scanning tunneling microscopy break junction(STM-BJ)technique,we have developed a“direct contact”approach to fabrication and investigation of the charge transport through single-cluster junctions of AgCu bimetallic metal clusterswith different halide anchors.Wefound that the electrodes could make contact directly with the surface halides of the single-cluster junctions and experience different contact resistance from different halogen atoms.Experiments and calculations reveal that the halide anchors provided efficient coupling between the cluster and the electrode,and the enhanced coupling with various halide anchors promoted electron transport and improved transmission probability.Our work offers a“direct contact”strategy for interface design between clusters of noble metals and electrodes,an essential step in progress toward single-cluster electronics.
基金supported by the National Key Research and Development Project(2022YFA1503900,2022YFA1503000,and 2022YFA1203400)Shenzhen Fundamental Research Funding(JCYJ20210324115809026,JCYJ20220818100212027,and JCYJ20200109141216566)+7 种基金Shenzhen Science and Technology Program(KQTD20190929173815000)Guangdong scientific program with contract no.2019QN01L057Guangdong Innovative and Entrepreneurial Research Team Program(2019ZT08C044)to Gu Msupported by the National Natural Science Foundation of China(22033005)to Li Jpartially sponsored by Guangdong Provincial Key Laboratory of Catalysis(2020B121201002).support from Presidential fund and Development and Reform Commission of Shenzhen Municipalitysupported by the Center for Computational Science and Engineering at SUSTechthe CHEM high-performance supercomputer cluster(CHEMHPC)located at the Department of Chemistry,SUSTech。
基金the 2022 Youth Scientific Research Fund Project of Qinghai University(No.2022-QGY-2)Qinghai Provincial Key Laboratory of New Light Alloys(No.2022-ZJY20)Kunlun Talent Project Program of Qinghai Province.
文摘Single cluster catalysts(SCCs),which exhibit remarkable catalytic performance due to their high metal loading and synergy effect between metal atoms,have attracted great attention in research.Herein,by means of density functional theory calculations,the oxygen reduction reaction(ORR),oxygen evolution reaction(OER),hydrogen evolution reaction(HER)performances of precious metal(Pt,Pd,Rh,Ir)trimetallic single-cluster electrocatalyst(U_(x)V_(y)W_(z)-NG)are investigated.The calculation results show that Pt,Pd,Ir have significant effect on ORR,OER,HER,respectively,all the calculated U_(x)V_(y)W_(z)-NG structures are thermodynamically stable due to the negative formation energies and binding energies.The Pt_(3)-NG,Pd_(3)-NG,Ir_(3)-NG show the lowest ORR,OER,HER overpotentials of 0.63,0.77,−0.02 V,respectively,among all combinations of U_(x)V_(y)W_(z)-NG.These overpotentials are lower than that of precious metal single atom catalysts(SACs),which indicate better activities of precious trimetallic SCCs than those of SACs.The electronic structure reveals that the O-2p orbital shows strong hybridization strength with Pt-3d orbitals in the system of OH adsorbed Pt_(3)-NG and thus facilitates the electrocatalytic reactions.The results are helpful for the rational design of high-performance triatomic catalysts.
基金financially supported by the National Key Research and Development Program of China(No.2018YFB0704300)the National Natural Science Foundation of China(Project Nos.21776248,21676246,and 21803074)+2 种基金Ning Bo S&T Innovation 2025 Major Special Programme(No.2018B10016)Zhejiang Provincial Natural Science Foundation of China(Grant No.LR17B060003)Fundamental Research Funds for the Central Universities(Grant No.2020XZZX002-07)。
文摘Electrochemical nitrogen reduction reaction(NRR)is one of the most promising alternatives to the traditional Haber-Bosch process.Designing efficient electrocatalysts is still challenging.Inspired by the recent experimental and theoretical advances on single-cluster catalysts(SCCs),we systematically investigated the catalytic performance of various triple-transition-metal-atom clusters anchored on nitrogen-doped graphene for NRR through density functional theory(DFT)calculation.Among them,Mn_(3)-N4,Fe_(3)-N4,Co_(3)-N4,and Mo_(3)-N4 were screened out as electrocatalysis systems composed of non-noble metal with high activity,selectivity,stability,and feasibility.Particularly,the Co_(3)-N4 possesses the highest activity with a limiting potential of-0.41 V through the enzymatic mechanism.The outstanding performance of Co_(3)-N4 can be attributed to the unique electronic structure leading to strong π backdonation,which is crucial in effective N_(2) activation.This work not only predicts four efficient non-noble metal electrocatalysts for NRR,but also suggest the SCCs can serve as potential candidates for other important electrochemical reactions.
基金financially supported by the National Natural Science Foundation of China(Nos.21771182,21501177 and 21673240)the Guangdong Innovation Research Team for Higher Education(No.2017KCXTD030)+1 种基金the High-level Talents Project of Dongguan University of Technology(No.KCYKYQD2017017)the Open Project Program of the State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences(No.20200006)。
文摘Confined metal clusters as sub-nanometer reactors for electrocatalytic N_(2) reduction reaction(eNRR)have received increasing attention due to the unique metal-metal interaction and higher activity than singleatom catalysts.Herein,the inspiration of the superior capacitance and unique microenvironment with regular surface cavities of the porous boron nitride(p-BN)nanosheets,we systematically studied the catalytic activity for NRR of transition-metal single-clusters in the triplet form(V_(3),Fe_(3),Mo_(3) and W_(3))confined in the surface cavities of the p-BN sheets by spin-polarized density functional theory(DFT)calculations.After a two-step screening strategy,Mo_(3)@p-BN was found to have high catalytic activity and selectivity with a rather low limiting potential(-0.34 V)for the NRR.The anchored Mo_(3) singlecluster can be stably embedded on the surface cavities of the substrate preventing the diffusion of the active Mo atoms.More importantly,the Mo atoms in the Mo_(3) single-cluster would act as“cache”to accelerate electron transfer between active metal centers and nitrogen-containing intermediates via the intimate Mo-Mo interactions.The cooperation of Mo atoms can also provide a large number of occupied and unoccupied d orbitals to make the"donation-backdonation"mechanism more effective.This work not only provides a quite promising electrocatalyst for NRR,but also brings new insights into the rational design of triple-atom NRR catalysts.
文摘A novel (Me 3PhCH 2N) 2[MoFe 4S 4(SC 6H 11 ) 7] cubane like cluster was obtained from a reaction system including (NH 4) 2MoS 4, FeCl 2 and NaSC 6H 11 in methanol, and characterized by X ray crystallography. The title compound crystallizes in triclinic space group P 1 with a =1.523 1(3), b =1.610 5(3), c =1.838 3(4) nm, α =77.18 (3)°, β =75.17(3)°, γ =64.60 (3)°, and Z =2. Also included in this paper are the discussions on the variation of the reaction products obtained from the participation of cyclohexylthiolate and on the changes of the structural features of the products.
