Developing highly active alloy catalysts that surpass the performance of platinum group metals in the oxygen reduction reaction(ORR)is critical in electrocatalysis.Gold-based single-atom alloy(AuSAA)clusters are gaini...Developing highly active alloy catalysts that surpass the performance of platinum group metals in the oxygen reduction reaction(ORR)is critical in electrocatalysis.Gold-based single-atom alloy(AuSAA)clusters are gaining recognition as promising alternatives due to their potential for high activity.However,enhancing its activity of AuSAA clusters remains challenging due to limited insights into its actual active site in alkaline environments.Herein,we studied a variety of Au_(54)M_(1) SAA cluster catalysts and revealed the operando formed MO_(x)(OH)_(y) complex acts as the crucial active site for catalyzing the ORR under the basic solution condition.The observed volcano plot indicates that Au_(54)Co_(1),Au_(54)M_(1),and Au_(54)Ru_(1) clusters can be the optimal Au_(54)M_(1) SAA cluster catalysts for the ORR.Our findings offer new insights into the actual active sites of AuSAA cluster catalysts,which will inform rational catalyst design in experimental settings.展开更多
Well-defined gold nanoclusters with average size less than 2 nm have emerged as a new and novel catalyst. The gold nanocluster loaded on the oxide surface usually aggregates to larger particles at high temperature （...Well-defined gold nanoclusters with average size less than 2 nm have emerged as a new and novel catalyst. The gold nanocluster loaded on the oxide surface usually aggregates to larger particles at high temperature （〉 300℃）, which is caused by the removal of the surface ligands. We herein pre-sent a novel method to prepare Au25cluster catalyst （-1.3 nm） with high thermal stability （up to 400℃）. Au25@Si02 is synthesized via a co-hydrolyzing reaction of Au2s[SC3H6Si（OCH3）3118 and tet-raethyl orthosilicate, and then it is treated at different temperature （e.g., 200, 300, 400℃） in air to remove the organic ligands. Au25@SiO2 is well characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and diffuse reflectance UV-vis spectroscopy. Further, the Au2s@SiO2 catalysts are investigated in the hydrogenation ofp-nitrophenol into p-aminophenol.展开更多
We used a dielectric barrier discharge(DBD)plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters.We used X-ray powder diffraction,ultraviolet-visible spectrophotometry,th...We used a dielectric barrier discharge(DBD)plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters.We used X-ray powder diffraction,ultraviolet-visible spectrophotometry,thermogravimetric analysis,and high angle annular dark-field-scanning transmission electron microscopy characterization to show that the samples pretreated with/without DBD-plasma displayed different performances in CO oxidation.The enhanced activity was obtained on the plasma-treated samples,implying that the protective ligand was effectively removed via the plasma technique.The crystal structure of the plasma-treated samples changed markedly,suggesting that the plasma treatment could not only break the chemical bond between the gold and the protective agent but could also decompose the interlayer ions over the hydrotalcite support.The particle sizes of the gold after DBD-plasma treatment implied that it was a good way to control the size of the gold nanoparticles under mild conditions.展开更多
The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in th...The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.展开更多
This review summarizes a variety of experimentally identified gas‐phase catalytic cycles,all of which are mediated by atomic metal ions,bare metal clusters,metal oxide clusters or metal complexes.Emphasis is placed o...This review summarizes a variety of experimentally identified gas‐phase catalytic cycles,all of which are mediated by atomic metal ions,bare metal clusters,metal oxide clusters or metal complexes.Emphasis is placed on the latest advances in the unique catalytic reactivity of cluster‐confined single noble metal atoms.The cycles discussed in this paper cover a wide range of inorganic and organic molecules.The use of start‐of‐the‐art mass spectrometric instrumentation in conjunction with quantum chemistry calculations is also reported,as these techniques have determined the mechanistic details of the elementary steps of such catalytic cycles.The important role of gas‐phase data in guiding the rational design of better‐performing catalysts in related condensed phase reactions is also examined.In particular,this review focuses on the following three topics:(1)the catalytic oxidation of carbon monoxide,(2)the catalytic functionalization of methane,and(3)catalytic decarboxylation.展开更多
Atomically precise gold nanoclusters have recently attracted intensive attention due to their significance in catalysis,chemical sensing,and bio-application.These nanoclusters often possess unique optical,chemical or ...Atomically precise gold nanoclusters have recently attracted intensive attention due to their significance in catalysis,chemical sensing,and bio-application.These nanoclusters often possess unique optical,chemical or physical properties originated from the quantum size effect（i.e.size andshapemorphology）.展开更多
Based on the short-range order,it is found that the abundance of the P-centered P-transition-metal clusters are the common feature among the liquid Pd-Cu-Ni-P alloys,and hence this feature alone could not uncover the ...Based on the short-range order,it is found that the abundance of the P-centered P-transition-metal clusters are the common feature among the liquid Pd-Cu-Ni-P alloys,and hence this feature alone could not uncover the underlying mechanisms of the variation of glass forming ability among the liquid alloys.For the so called similar elements such as Cu and Ni,their behaviors are significantly different when interacting with Pd or P atoms.Cu has weak bonding with both Pd and P while Ni has very strong bonding with P but nearly no bonding with Pd.The different bonding characters thus underlie the phenomenon that in the best glass formers the ratio of the two similar elements often deviates from 1:1.Only if the parameters of chemical short-range order of Cu and Ni around P become closest to each other the best glass forming ability is reached.It is also illustrated that the calculated dynamic properties are very helpful to locate the composition of the best glass former.展开更多
文摘Developing highly active alloy catalysts that surpass the performance of platinum group metals in the oxygen reduction reaction(ORR)is critical in electrocatalysis.Gold-based single-atom alloy(AuSAA)clusters are gaining recognition as promising alternatives due to their potential for high activity.However,enhancing its activity of AuSAA clusters remains challenging due to limited insights into its actual active site in alkaline environments.Herein,we studied a variety of Au_(54)M_(1) SAA cluster catalysts and revealed the operando formed MO_(x)(OH)_(y) complex acts as the crucial active site for catalyzing the ORR under the basic solution condition.The observed volcano plot indicates that Au_(54)Co_(1),Au_(54)M_(1),and Au_(54)Ru_(1) clusters can be the optimal Au_(54)M_(1) SAA cluster catalysts for the ORR.Our findings offer new insights into the actual active sites of AuSAA cluster catalysts,which will inform rational catalyst design in experimental settings.
基金supported by the National Natural Science Foundation of China (21273231, 21422308)Dalian Excellent Youth Foundation (2014J11JH126) (FW)the Starting Funds of “Thousand Youth Talents Plan” (GL)~~
文摘Well-defined gold nanoclusters with average size less than 2 nm have emerged as a new and novel catalyst. The gold nanocluster loaded on the oxide surface usually aggregates to larger particles at high temperature （〉 300℃）, which is caused by the removal of the surface ligands. We herein pre-sent a novel method to prepare Au25cluster catalyst （-1.3 nm） with high thermal stability （up to 400℃）. Au25@Si02 is synthesized via a co-hydrolyzing reaction of Au2s[SC3H6Si（OCH3）3118 and tet-raethyl orthosilicate, and then it is treated at different temperature （e.g., 200, 300, 400℃） in air to remove the organic ligands. Au25@SiO2 is well characterized by transmission electron microscopy, ultraviolet-visible spectroscopy and diffuse reflectance UV-vis spectroscopy. Further, the Au2s@SiO2 catalysts are investigated in the hydrogenation ofp-nitrophenol into p-aminophenol.
文摘We used a dielectric barrier discharge(DBD)plasma technique to eliminate the protective ligand of ZnAl-hydrotalcite-supported gold nanoclusters.We used X-ray powder diffraction,ultraviolet-visible spectrophotometry,thermogravimetric analysis,and high angle annular dark-field-scanning transmission electron microscopy characterization to show that the samples pretreated with/without DBD-plasma displayed different performances in CO oxidation.The enhanced activity was obtained on the plasma-treated samples,implying that the protective ligand was effectively removed via the plasma technique.The crystal structure of the plasma-treated samples changed markedly,suggesting that the plasma treatment could not only break the chemical bond between the gold and the protective agent but could also decompose the interlayer ions over the hydrotalcite support.The particle sizes of the gold after DBD-plasma treatment implied that it was a good way to control the size of the gold nanoparticles under mild conditions.
文摘The structure, spectroscopic properties and chemical stability of [VS4-(CuPPh3)3 (CuCl)Br2] in CDCl3 solution have been studied by multinuclear NMR tech-nique. Two peaks with relative intensity of 1: 4 are found in the31P-{1H} spectra.Some 13C-{1H} and 1H NMR peaks have the same integral intensity ratio. These com-plemented the results of 31P-{1H} NMR. The experimental results demonstrates that the PPh3 ligand bound to Cu(6) is not equivalent with the four PPh3 ligands bound toCu(2) ~Cu (5 )- It affords an evidence that the title compound in the solution keepssimilar structure to solid state.
基金supported by the National Natural Science Foundation of China(21303215,21325215,21573246)the Major Research Plan of China(No.2013CB834603)the grant from the Youth Innovation Promotion Association,Chinese Academy of Sciences(2016030)~~
文摘This review summarizes a variety of experimentally identified gas‐phase catalytic cycles,all of which are mediated by atomic metal ions,bare metal clusters,metal oxide clusters or metal complexes.Emphasis is placed on the latest advances in the unique catalytic reactivity of cluster‐confined single noble metal atoms.The cycles discussed in this paper cover a wide range of inorganic and organic molecules.The use of start‐of‐the‐art mass spectrometric instrumentation in conjunction with quantum chemistry calculations is also reported,as these techniques have determined the mechanistic details of the elementary steps of such catalytic cycles.The important role of gas‐phase data in guiding the rational design of better‐performing catalysts in related condensed phase reactions is also examined.In particular,this review focuses on the following three topics:(1)the catalytic oxidation of carbon monoxide,(2)the catalytic functionalization of methane,and(3)catalytic decarboxylation.
文摘Atomically precise gold nanoclusters have recently attracted intensive attention due to their significance in catalysis,chemical sensing,and bio-application.These nanoclusters often possess unique optical,chemical or physical properties originated from the quantum size effect（i.e.size andshapemorphology）.
基金supported by the National Natural Science Foundation of China (Grant Nos. 50971082 and 50831003)
文摘Based on the short-range order,it is found that the abundance of the P-centered P-transition-metal clusters are the common feature among the liquid Pd-Cu-Ni-P alloys,and hence this feature alone could not uncover the underlying mechanisms of the variation of glass forming ability among the liquid alloys.For the so called similar elements such as Cu and Ni,their behaviors are significantly different when interacting with Pd or P atoms.Cu has weak bonding with both Pd and P while Ni has very strong bonding with P but nearly no bonding with Pd.The different bonding characters thus underlie the phenomenon that in the best glass formers the ratio of the two similar elements often deviates from 1:1.Only if the parameters of chemical short-range order of Cu and Ni around P become closest to each other the best glass forming ability is reached.It is also illustrated that the calculated dynamic properties are very helpful to locate the composition of the best glass former.
