Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalit...Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.展开更多
A series of Al‐containing mesostructured cellular silica foams(Al‐MCFs)with different Si/Al molar ratios(x;x=10,20,30,40,or50)were prepared by a post synthetic method using aluminum isopropoxide as an alumina source...A series of Al‐containing mesostructured cellular silica foams(Al‐MCFs)with different Si/Al molar ratios(x;x=10,20,30,40,or50)were prepared by a post synthetic method using aluminum isopropoxide as an alumina source.The corresponding NiMo catalysts supported on Al‐MCFs were prepared and evaluated using dibenzothiophene(DBT)as the probe reactant.All the synthesized samples were characterized by small‐angle X‐ray scattering,scanning electron microscopy,nitrogen adsorption‐desorption,UV‐Vis diffuse reflectance spectroscopy,H2temperature‐programmed reduction,27Al MAS NMR,temperature‐programmed desorption of ammonia,pyridine‐FTIR,Raman spectroscopy,HRTEM,and X‐ray photoelectron spectroscopy to analyze their physicochemical properties and to gain a deeper insight of the interrelationship between the structures and the catalytic performance.The synthesis mechanism was proposed to involve the formation of Br?nsted acid and Lewis acid sites through the replacement of Si4+with Al3+.Aluminum introduced into MCFs by the post synthetic method has a negligible influence on the mesostructure of the parent MCFs but can form silicoaluminate materials with moderate Br?nsted acidity.For Al‐MCFs(x)materials,the detection of tetrahedrally coordinated Al3+cations demonstrated that the Al species had been successfully incorporated into the silicon frameworks.Furthermore,the DBT hydrodesulfurization(HDS)catalytic activity of the NiMo/Al‐MCFs(x)catalysts increased with increasing Si/Al molar ratio,and reached a maximum at a Si/Al molar ratio of20.The interaction of Ni and Mo species with the support became stronger when Al was incorporated into the MCFs supports.The high activities of the NiMo/Al‐MCFs catalysts for the DBT HDS were attributed to the suitable acidity properties and good dispersions of the Ni and Mo active phases.展开更多
基金supported by the open funds of Key Laboratory of Functional Inorganic Material Chemistry (Heilongjiang University), Ministry of Education, Chinathe funding from Guangdong Natural Science Funds (No. 2023A0505050107)。
文摘Atomically precise metal nanoclusters are an emerging type of nanomaterial which has diverse interfacial metal-ligand coordination motifs that can significantly affect their physicochemical properties and functionalities.Among that,Cu nanoclusters have been gaining continuous increasing research attentions,thanks to the low cost,diversified structures,and superior catalytic performance for various reactions.In this review,we first summarize the recent progress regarding the synthetic methods of atomically precise Cu nanoclusters and the coordination modes between Cu and several typical ligands and then discuss the catalytic applications of these Cu nanoclusters with some explicit examples to explain the atomical-level structure-performance relationship.Finally,the current challenges and future research perspectives with some critical thoughts are elaborated.We hope this review can not only provide a whole picture of the current advances regarding the synthesis and catalytic applications of atomically precise Cu nanoclusters,but also points out some future research visions in this rapidly booming field.
基金supported by National Natural Science Foundation of China (21276277,U1463207)CNOOC Project+1 种基金CNPC major projectthe Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology (2015K003)~~
文摘A series of Al‐containing mesostructured cellular silica foams(Al‐MCFs)with different Si/Al molar ratios(x;x=10,20,30,40,or50)were prepared by a post synthetic method using aluminum isopropoxide as an alumina source.The corresponding NiMo catalysts supported on Al‐MCFs were prepared and evaluated using dibenzothiophene(DBT)as the probe reactant.All the synthesized samples were characterized by small‐angle X‐ray scattering,scanning electron microscopy,nitrogen adsorption‐desorption,UV‐Vis diffuse reflectance spectroscopy,H2temperature‐programmed reduction,27Al MAS NMR,temperature‐programmed desorption of ammonia,pyridine‐FTIR,Raman spectroscopy,HRTEM,and X‐ray photoelectron spectroscopy to analyze their physicochemical properties and to gain a deeper insight of the interrelationship between the structures and the catalytic performance.The synthesis mechanism was proposed to involve the formation of Br?nsted acid and Lewis acid sites through the replacement of Si4+with Al3+.Aluminum introduced into MCFs by the post synthetic method has a negligible influence on the mesostructure of the parent MCFs but can form silicoaluminate materials with moderate Br?nsted acidity.For Al‐MCFs(x)materials,the detection of tetrahedrally coordinated Al3+cations demonstrated that the Al species had been successfully incorporated into the silicon frameworks.Furthermore,the DBT hydrodesulfurization(HDS)catalytic activity of the NiMo/Al‐MCFs(x)catalysts increased with increasing Si/Al molar ratio,and reached a maximum at a Si/Al molar ratio of20.The interaction of Ni and Mo species with the support became stronger when Al was incorporated into the MCFs supports.The high activities of the NiMo/Al‐MCFs catalysts for the DBT HDS were attributed to the suitable acidity properties and good dispersions of the Ni and Mo active phases.
