To reduce the difficulty of material filling into the top region of tooth in hot precision forging of gears using the alternative die designs, relief-cavity designs in different sizes were performed on the top of die ...To reduce the difficulty of material filling into the top region of tooth in hot precision forging of gears using the alternative die designs, relief-cavity designs in different sizes were performed on the top of die tooth. The influences of the conventional process and relief-cavity designs on corner filling, workpiece stress, die stress, forming load and material utilization were examined. Finite element simulation for tooth forming, die stress and forming load using the four designs was performed. The material utilization was further considered, and the optimal design was determined. The tooth form and forming load in forging trials ensured the validity of FE simulation. Tooth accuracy was inspected by video measuring machine(VMM), which shows the hot forged accuracy achieves the level of rough machining of gear teeth. The effects of friction on mode of metal flow and strain distribution were also discussed.展开更多
To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO...To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO_(2) RR) is involved with multiple electrons and multiple products,plus the complexity of the surface chemical environment of the catalyst,it is extremely challenging to establish the structure/function relationship.Atomically precise metal nanoclusters(NCs),with crystallographically resolved structure,molecule-like characters and strong quantum confinement effects,have been emerging as a new type of catalyst for CO_(2) RR,and more importantly,they can provide an ideal platform to unravel the comprehensive mechanistic insights and establish the structure/function relationship eventually.In this review,the recent advances regarding employing molecular metal NCs with well-defined structure including Au NCs,Au-based alloy NCs,Ag NCs,Cu NCs for CO_(2) RR and relevant mechanistic studies are discussed,and the opportunities and challenges are proposed at the end for paving the development of CO_(2) RR by using atomically precise metal NCs.展开更多
The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.H...The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.展开更多
The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-ba...The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.展开更多
Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescen...Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescence,thermocatalysis,electrocatalysis,photocatalysis,magnetism,and optical activity.Over the past several decades,there has been tremendous progress in our understanding of the structure and physicochemical properties of Aun(SR)m NCs,resulting in the ability to fine-tune the characteristics of these materials.It is therefore helpful to examine the extent to which the properties of Aun(SR)m and related metal NCs can now be adjusted based on design.This review presents representative examples of previous studies concerning the geometry,electronic structure,luminescence properties,catalysis,magnetism and optical activity of Aun(SR)m and related metal NCs and discusses the current status of the designability of these NCs to impart specific structural and physicochemical characteristics.This information is expected to accelerate the fabrication of highly functional materials based on Aun(SR)m and related metal NCs.展开更多
基金Project(51375042)supported by the National Natural Science Foundation of ChinaProject supported by Beijing Laboratory of Modern Transport Metal Materials and Processing Technology,China
文摘To reduce the difficulty of material filling into the top region of tooth in hot precision forging of gears using the alternative die designs, relief-cavity designs in different sizes were performed on the top of die tooth. The influences of the conventional process and relief-cavity designs on corner filling, workpiece stress, die stress, forming load and material utilization were examined. Finite element simulation for tooth forming, die stress and forming load using the four designs was performed. The material utilization was further considered, and the optimal design was determined. The tooth form and forming load in forging trials ensured the validity of FE simulation. Tooth accuracy was inspected by video measuring machine(VMM), which shows the hot forged accuracy achieves the level of rough machining of gear teeth. The effects of friction on mode of metal flow and strain distribution were also discussed.
基金the grant from the National Natural Science Foundation of China(No.21805170)financial support from Guangdong Natural Science Funds for Distinguished Young Scholars(No.2015A030306006)+1 种基金Guangzhou Science and Technology Plan Projects(No.201804010323)the fundamental funds for central universities(SCUT No.2018ZD022)。
文摘To alleviate the global warming by removing excess CO_(2) and converting them into value-added chemicals,(photo)electrochemical reduction has been recognized as a promising strategy.As the CO_(2) reduction reaction(CO_(2) RR) is involved with multiple electrons and multiple products,plus the complexity of the surface chemical environment of the catalyst,it is extremely challenging to establish the structure/function relationship.Atomically precise metal nanoclusters(NCs),with crystallographically resolved structure,molecule-like characters and strong quantum confinement effects,have been emerging as a new type of catalyst for CO_(2) RR,and more importantly,they can provide an ideal platform to unravel the comprehensive mechanistic insights and establish the structure/function relationship eventually.In this review,the recent advances regarding employing molecular metal NCs with well-defined structure including Au NCs,Au-based alloy NCs,Ag NCs,Cu NCs for CO_(2) RR and relevant mechanistic studies are discussed,and the opportunities and challenges are proposed at the end for paving the development of CO_(2) RR by using atomically precise metal NCs.
基金financially supported by the National Natural Science Foundation of China(Nos.92061110,21925303,21829501,21771186,21222301,21528303,and 21171170)the Anhui Provincial Natural Science Foundation(2108085Y05 and 2108085MB56)+1 种基金Collaborative Innovation Program of Hefei Science Center,CAS(Nos.2020HSCCIP005 and 2022HSC-CIP018)the Hefei National Laboratory for Physical Sciences at the Microscale(KF2020102).
文摘The emergence of metal nanoclusters with atomically precise compositions and structures provides an opportunity for in-depth investigation of catalysis mechanisms and structure−property correlations at the nanoscale.However,a serious problem for metal nanocluster catalysts is that the ligands inhibit the catalytic activity through deactivating the surface of the nanoclusters.Here,we introduce a novel catalytic mode for metal nanoclusters,in which the nanoclusters initiate the catalysis via single electron transfer(SET)without destroying the integrity of nanoclusters,providing a solution for the contradiction between activity and stability of metal nanoclusters.We illustrated that the novel activation mode featured low catalyst loading(0.01 mol%),high TOF,mild reaction conditions,and easy recycling of catalyst in alkyne hydroborylation,which often suffered from poor selectivity,low functional group tolerance,etc.Furthermore,the catalyst[Au_(1)Cu_(14)(TBBT)_(12)(PPh_(3))_(6)]^(+)(TBBTH:p-tert-butylthiophenol)can be applied in highly efficient tandem processes such as hydroborylation−deuteration and hydroborylation−isomerization,demonstrating the utility of the introduced activation mode for metal nanoclusters.
基金the Natural Science research project of Universities in Anhui Province(No.KJ2021ZD0001)the Natural Science Foundation of Anhui Province(No.2208085MB20)the National Natural Science Foundation of China(No.22101001).
文摘The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.
基金Japan Society for the Promotion of Science,Grant/Award Numbers:20H02698,20H02552,18H05178,20H05115Hydrogenomics,Grant/Award Number:21H00027+7 种基金Aquatic Functional Materials,Grant/Award Numbers:18H05178,22H04562Yazaki Memorial Foundation for Science and TechnologyOgasawara Foundation for the Promotion of Science and EngineeringKao Foundation for Arts and SciencesTEPCO Memorial FoundationJapan Science SocietyTakahashi Industrial and Economic Research FoundationKubota Corporation。
文摘Thiolate(SR)-protected gold nanoclusters(Aun(SR)m NCs)are a rare type of material capable of simultaneously exhibiting multiple physicochemical properties well-suited to specific applications,including photoluminescence,thermocatalysis,electrocatalysis,photocatalysis,magnetism,and optical activity.Over the past several decades,there has been tremendous progress in our understanding of the structure and physicochemical properties of Aun(SR)m NCs,resulting in the ability to fine-tune the characteristics of these materials.It is therefore helpful to examine the extent to which the properties of Aun(SR)m and related metal NCs can now be adjusted based on design.This review presents representative examples of previous studies concerning the geometry,electronic structure,luminescence properties,catalysis,magnetism and optical activity of Aun(SR)m and related metal NCs and discusses the current status of the designability of these NCs to impart specific structural and physicochemical characteristics.This information is expected to accelerate the fabrication of highly functional materials based on Aun(SR)m and related metal NCs.