Nanoparticles(NPs)play a vital role in the energy catalysis process,so understanding the heterogeneous catalytic properties of nanocatalysts is of great significance for rationally guiding the design of catalysts.Howe...Nanoparticles(NPs)play a vital role in the energy catalysis process,so understanding the heterogeneous catalytic properties of nanocatalysts is of great significance for rationally guiding the design of catalysts.However,the traditional method obtains the average information based on the whole and cannot study the catalytic activity of a single nanoparticle.It is critical to investigate the catalytic activity of individual nanoparticles using in situ techniques.This review summarizes some of Prof.Xu's recent accomplishments in studying the catalytic behavior of nanoparticles at the single-particle level using single-molecule fluorescence microscopy(SMFM).These achievements include revealing the effect of size,shape,and surface atoms of Pd nanoparticles on catalytic kinetics and dynamics as well as obtaining the activation energy of single Au nanoparticles for catalytic reactions by single-molecule methods.It is the first time to study the kinetics and dynamics of single-atom Pt catalysts.Furthermore,the method was extended to study the Pt deactivation process for hydrogen oxidation reactions as well as the catalytic kinetics of two-electron oxygen reduction reactions of individual Fe3O4 nanoparticles in electrocatalysis.Finally,single-molecule super-resolution techniques were used to observe the evolution of the activity of single Sb doped TiO2 nanorod domains.These studies are of guiding significance for in-depth understanding and realization of rational design of optimal catalysts.展开更多
Studying the activity of individual nanocata- lysts, especially with high spatiotemporal resolution of single-molecule and single-turnover scale, is essential for the understanding of catalytic mechanism and the desig...Studying the activity of individual nanocata- lysts, especially with high spatiotemporal resolution of single-molecule and single-turnover scale, is essential for the understanding of catalytic mechanism and the designing of effective catalysts. Several approaches have been developed to monitor the catalytic reaction on single catalysts. In this review, we summarized the updated progresses of several new spectroscopic and microscopic approaches, including single-molecule fluorescence microscopy, surface-enhanced Raman spectroscopy, surface plasmon resonance microscopy and X-ray microscopy, for the study of single-molecule and single-particle catalysis.展开更多
This study explores how zirconia additive interacts with MgH_(2)to improve its hydrogen storage performance.Initially it is confirmed that the zirconia added MgH_(2)powder releases hydrogen at a temperature of about 5...This study explores how zirconia additive interacts with MgH_(2)to improve its hydrogen storage performance.Initially it is confirmed that the zirconia added MgH_(2)powder releases hydrogen at a temperature of about 50℃below that of the additive free MgH_(2).Subsequent tests by X ray diffraction(XRD)and infrared(IR)spectroscopy techniques reveal that the ZrO_(2) mixed MgH_(2)powder contains ZrHx(2<x>1.5)and MgO secondary phases.This observation is supported by the negative Gibbs free energy values obtained for the formation of ZrH_(2)/MgO from ZrO_(2)/MgH_(2)powder samples.An X ray photoelectron spectroscopy(XPS)study reveals that apart from Zr^(4+)cations,Zr^(2+) and zero valent Zr exist in the powder.Atomic force microscopy(AFM)study reveals that the average grain size is 20 nm and the elemental line scan profiles further proves the existence of oxygen deficient Zr bearing phase(s).This study strengthens the belief that functional metal oxide additives in fact chemically interact with MgH_(2)to make active in-situ catalysts in the MgH_(2)system.展开更多
A ligand-free Heck reaction catalyzed by in situ-generated palladium nanoparticles in PEG-400 has been developed.This catalytic system is a simple and active protocol for the Heck reaction of aryl halides under mild c...A ligand-free Heck reaction catalyzed by in situ-generated palladium nanoparticles in PEG-400 has been developed.This catalytic system is a simple and active protocol for the Heck reaction of aryl halides under mild conditions.Comparative experiments demonstrated that the Heck reaction catalyzed by the palladium nanoparticles in situ-generated under the Heck reaction conditions was carried out much quicker than that by the in ex situ-generated ones.展开更多
Ti-based catalysts are known to improve the hydrogen storage performance of NaAlH4by facilitating the dissociation/recombination of H-H and Al-H bonds.The catalytic activity of metallic Ti species strongly depends on ...Ti-based catalysts are known to improve the hydrogen storage performance of NaAlH4by facilitating the dissociation/recombination of H-H and Al-H bonds.The catalytic activity of metallic Ti species strongly depends on its particle size and dispersity.Ti clusters and even single atoms are therefore highly desirable,but their controllable fabrication has been highly challenging.He rein,we demonstrate a novel facile sonochemical synthesis of a Ti-O clusters featuring single Ti atom catalyst at room temperature.Through reducing TiCl_(4)by MgBu_(2)with ultrasound instead of heating as driving force,numerous single Ti atoms coupled with Ti-O clusters with Ti loading on graphene(Ti_(1)/Ti-O@G)up to 22.6 wt%have been successfully obtained.The prepared Ti_(1)/Ti-O@G contributes high reactivity and superior catalytic activity,therefore enabling full dehydrogenation of NaAlH_(4)at 80℃in thermogravimetric mode and re-hydrogenation at 30℃and 10 MPa with 4.9 wt% H_(2).This fact indicates for the first time that single Ti atom catalyst with high loading is highly effective in catalyzing hydrogen cycling of NaAlH4at remarkably reduced temperatures.展开更多
We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed...We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed the best activity. Small monodispersed Pd-Ni bimetallic nanoparticles were loaded on the surface of titanium oxide nanopowder as confirmed with TEM and EDS mapping. The XPS analysis demonstrated that Pd exists as 31% Pd(II) species and 69% Pd(0) species and all nickel is Ni(II). The prepared Pd-Ni/TiO2 exhibited enhanced catalytic activity compared to an equal amount of Pd/TiO2 for Suzuki-Miyaura reactions together with excellent applicability and reusability.展开更多
Nanogold particles of 10 nm were used to label goat anti-human IgG (GIgG) to obtain nanogold-labeled GIgG (AuGIgG). In a citrate-HCl buffer solution of pH 2.27,AuGIgG showed a strong catalytic effect on the reaction b...Nanogold particles of 10 nm were used to label goat anti-human IgG (GIgG) to obtain nanogold-labeled GIgG (AuGIgG). In a citrate-HCl buffer solution of pH 2.27,AuGIgG showed a strong catalytic effect on the reaction between HAuCl4 and NH2OH to form big gold particles that exhibited a resonance scatter-ing (RS) peak at 796 nm. Under the chosen conditions,AuGIgG combined with IgG to form immuno-complex AuGIgG-IgG that can be removed by centrifuging at 16000 r/min. AuGIgG in the centrifuging solution also showed catalytic effect on the reaction. On those grounds,an immunonanogold catalytic RS assay for IgG was designed. With addition of IgG,the amount of AuGIgG in the centrifuging solution decreased; the RS intensity at 796 nm (I796 nm) decreased linearly. The decreased intensity ΔI796 nm was linear with respect to the IgG concentration in the range of 0.08-16.0 ng·mL-1 with a detection limit of 0.02 ng·mL-1. This assay was applied to analysis of IgG in sera with satisfactory sensitivity,selectivity and rapidity.展开更多
Hydrogen is the most preferred choice as an energy source to replace the nonrenewable energy resources such as fossil fuels due to its beneficial features of abundance,ecofriendly,and outstanding gravimetric energy de...Hydrogen is the most preferred choice as an energy source to replace the nonrenewable energy resources such as fossil fuels due to its beneficial features of abundance,ecofriendly,and outstanding gravimetric energy density.Splitting water through a proton exchange membrane(PEM)electrolyzer is a well-known method of hydrogen production.But the major impediment is the sluggish kinetics of oxygen evolution reaction(OER).Currently,scientists are struggling to build out an acid-stable electrocatalyst for OER with low overpotential and excellent stability.In this review,the reaction mechanism and characterization parameters of OER are introduced,and then the improvement method of metal nanocatalysts(noble metal catalysts and noble metal-free catalysts)in acidic media is discussed.Particularly,the application of single-atom catalysts in acidic OER is summarized,which is current researching focus.At the same time,we also briefly introduced the cluster phenomenon,which is easy to occur in the preparation of single-atom catalysts.More importantly,we summarized the in situ characterization methods such as in situ X-ray absorption spectroscopy,in situ X-ray photoelectron spectroscopy,and so forth,which are conducive to further understanding of OER reaction intermediates and active sites.Finally,we put forward some opinions on the development of acidic OER.展开更多
The resonance scattering spectral technique has been established using the synchronous scanning technique on spectrofluorometry.Because of its advantages of simplicity,rapidity and sensitivity,it has been widely appli...The resonance scattering spectral technique has been established using the synchronous scanning technique on spectrofluorometry.Because of its advantages of simplicity,rapidity and sensitivity,it has been widely applied to analyses of proteins,nucleic acids and inorganic ions.This paper summarizes the application of immunonanogold and aptamer modified nanogold(AptAu) catalytic resonance scattering spectral technique in combination with the work of our group,citing 53 references.展开更多
Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular l...Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21925205,22072145,21733004,and 21721003)the National Key Research and Development Program of China(Nos.2017YFE9127900 and 2018YFB1502302)K.C.Wong Education Foundation and Science.
文摘Nanoparticles(NPs)play a vital role in the energy catalysis process,so understanding the heterogeneous catalytic properties of nanocatalysts is of great significance for rationally guiding the design of catalysts.However,the traditional method obtains the average information based on the whole and cannot study the catalytic activity of a single nanoparticle.It is critical to investigate the catalytic activity of individual nanoparticles using in situ techniques.This review summarizes some of Prof.Xu's recent accomplishments in studying the catalytic behavior of nanoparticles at the single-particle level using single-molecule fluorescence microscopy(SMFM).These achievements include revealing the effect of size,shape,and surface atoms of Pd nanoparticles on catalytic kinetics and dynamics as well as obtaining the activation energy of single Au nanoparticles for catalytic reactions by single-molecule methods.It is the first time to study the kinetics and dynamics of single-atom Pt catalysts.Furthermore,the method was extended to study the Pt deactivation process for hydrogen oxidation reactions as well as the catalytic kinetics of two-electron oxygen reduction reactions of individual Fe3O4 nanoparticles in electrocatalysis.Finally,single-molecule super-resolution techniques were used to observe the evolution of the activity of single Sb doped TiO2 nanorod domains.These studies are of guiding significance for in-depth understanding and realization of rational design of optimal catalysts.
文摘Studying the activity of individual nanocata- lysts, especially with high spatiotemporal resolution of single-molecule and single-turnover scale, is essential for the understanding of catalytic mechanism and the designing of effective catalysts. Several approaches have been developed to monitor the catalytic reaction on single catalysts. In this review, we summarized the updated progresses of several new spectroscopic and microscopic approaches, including single-molecule fluorescence microscopy, surface-enhanced Raman spectroscopy, surface plasmon resonance microscopy and X-ray microscopy, for the study of single-molecule and single-particle catalysis.
文摘This study explores how zirconia additive interacts with MgH_(2)to improve its hydrogen storage performance.Initially it is confirmed that the zirconia added MgH_(2)powder releases hydrogen at a temperature of about 50℃below that of the additive free MgH_(2).Subsequent tests by X ray diffraction(XRD)and infrared(IR)spectroscopy techniques reveal that the ZrO_(2) mixed MgH_(2)powder contains ZrHx(2<x>1.5)and MgO secondary phases.This observation is supported by the negative Gibbs free energy values obtained for the formation of ZrH_(2)/MgO from ZrO_(2)/MgH_(2)powder samples.An X ray photoelectron spectroscopy(XPS)study reveals that apart from Zr^(4+)cations,Zr^(2+) and zero valent Zr exist in the powder.Atomic force microscopy(AFM)study reveals that the average grain size is 20 nm and the elemental line scan profiles further proves the existence of oxygen deficient Zr bearing phase(s).This study strengthens the belief that functional metal oxide additives in fact chemically interact with MgH_(2)to make active in-situ catalysts in the MgH_(2)system.
基金The authors thank the financial support from State Key Laboratory of Fine Chemicals(No.KF0801)Science Research Foundation of DUT,Graduate Student Education Reform Fund of DUTthe National Natural Science Foundation of China(No.20976024).
文摘A ligand-free Heck reaction catalyzed by in situ-generated palladium nanoparticles in PEG-400 has been developed.This catalytic system is a simple and active protocol for the Heck reaction of aryl halides under mild conditions.Comparative experiments demonstrated that the Heck reaction catalyzed by the palladium nanoparticles in situ-generated under the Heck reaction conditions was carried out much quicker than that by the in ex situ-generated ones.
基金financially supported by the National Outstanding Youth Foundation of China(No.52125104)the Natural Science Foundation of Zhejiang Province(No.LD21E010002)+2 种基金the National Natural Science Foundation of China(Nos.52071285 and 52001277)the Fundamental Research Funds for the Central Universities(Nos.2021FZZX001-09 and 226-202200246)the National Youth Top-Notch Talent Support Program。
文摘Ti-based catalysts are known to improve the hydrogen storage performance of NaAlH4by facilitating the dissociation/recombination of H-H and Al-H bonds.The catalytic activity of metallic Ti species strongly depends on its particle size and dispersity.Ti clusters and even single atoms are therefore highly desirable,but their controllable fabrication has been highly challenging.He rein,we demonstrate a novel facile sonochemical synthesis of a Ti-O clusters featuring single Ti atom catalyst at room temperature.Through reducing TiCl_(4)by MgBu_(2)with ultrasound instead of heating as driving force,numerous single Ti atoms coupled with Ti-O clusters with Ti loading on graphene(Ti_(1)/Ti-O@G)up to 22.6 wt%have been successfully obtained.The prepared Ti_(1)/Ti-O@G contributes high reactivity and superior catalytic activity,therefore enabling full dehydrogenation of NaAlH_(4)at 80℃in thermogravimetric mode and re-hydrogenation at 30℃and 10 MPa with 4.9 wt% H_(2).This fact indicates for the first time that single Ti atom catalyst with high loading is highly effective in catalyzing hydrogen cycling of NaAlH4at remarkably reduced temperatures.
基金Acknowledgements We are grateful for financial support from the National Key R&D Program of China (Grant No. 2016YFA0202900), the National Natural Science Foundation of China (Grant Nos. 21376212 and 21436010).
文摘We have successfully prepared a series of Pd- Ni/TiO2 catalysts by a one-step impregnation-reduction method. Among these catalysts with different compositions of Ni and Pd, the one with the Ni:Pd ratio of 2.95 showed the best activity. Small monodispersed Pd-Ni bimetallic nanoparticles were loaded on the surface of titanium oxide nanopowder as confirmed with TEM and EDS mapping. The XPS analysis demonstrated that Pd exists as 31% Pd(II) species and 69% Pd(0) species and all nickel is Ni(II). The prepared Pd-Ni/TiO2 exhibited enhanced catalytic activity compared to an equal amount of Pd/TiO2 for Suzuki-Miyaura reactions together with excellent applicability and reusability.
基金the National Natural Science Foundation of China (Grant No. 20667001)Natural Science Foundation of Guangxi Province (Grant No. 0728213)the Foundation of New Century Ten-Hundred-Thousand Talents of Guangxi Province
文摘Nanogold particles of 10 nm were used to label goat anti-human IgG (GIgG) to obtain nanogold-labeled GIgG (AuGIgG). In a citrate-HCl buffer solution of pH 2.27,AuGIgG showed a strong catalytic effect on the reaction between HAuCl4 and NH2OH to form big gold particles that exhibited a resonance scatter-ing (RS) peak at 796 nm. Under the chosen conditions,AuGIgG combined with IgG to form immuno-complex AuGIgG-IgG that can be removed by centrifuging at 16000 r/min. AuGIgG in the centrifuging solution also showed catalytic effect on the reaction. On those grounds,an immunonanogold catalytic RS assay for IgG was designed. With addition of IgG,the amount of AuGIgG in the centrifuging solution decreased; the RS intensity at 796 nm (I796 nm) decreased linearly. The decreased intensity ΔI796 nm was linear with respect to the IgG concentration in the range of 0.08-16.0 ng·mL-1 with a detection limit of 0.02 ng·mL-1. This assay was applied to analysis of IgG in sera with satisfactory sensitivity,selectivity and rapidity.
基金National Natural Science Foundation of China,Grant/Award Number:21801015Beijing Institute of Technology Research Fund Program for Young Scholars,Grant/Award Number:3090012221909Fundamental Research Funds for the Central Universities。
文摘Hydrogen is the most preferred choice as an energy source to replace the nonrenewable energy resources such as fossil fuels due to its beneficial features of abundance,ecofriendly,and outstanding gravimetric energy density.Splitting water through a proton exchange membrane(PEM)electrolyzer is a well-known method of hydrogen production.But the major impediment is the sluggish kinetics of oxygen evolution reaction(OER).Currently,scientists are struggling to build out an acid-stable electrocatalyst for OER with low overpotential and excellent stability.In this review,the reaction mechanism and characterization parameters of OER are introduced,and then the improvement method of metal nanocatalysts(noble metal catalysts and noble metal-free catalysts)in acidic media is discussed.Particularly,the application of single-atom catalysts in acidic OER is summarized,which is current researching focus.At the same time,we also briefly introduced the cluster phenomenon,which is easy to occur in the preparation of single-atom catalysts.More importantly,we summarized the in situ characterization methods such as in situ X-ray absorption spectroscopy,in situ X-ray photoelectron spectroscopy,and so forth,which are conducive to further understanding of OER reaction intermediates and active sites.Finally,we put forward some opinions on the development of acidic OER.
基金support from the National Natural Science Foundation of China(20365001,20667001 & 20865002)the Natural Science Foundation of Guangxi(0832260 & 0991021z)the Foundation of New Century Ten-Hundred-Thousand Talents of Guangxi
文摘The resonance scattering spectral technique has been established using the synchronous scanning technique on spectrofluorometry.Because of its advantages of simplicity,rapidity and sensitivity,it has been widely applied to analyses of proteins,nucleic acids and inorganic ions.This paper summarizes the application of immunonanogold and aptamer modified nanogold(AptAu) catalytic resonance scattering spectral technique in combination with the work of our group,citing 53 references.
基金supported by the National Natural Science Foundation of China(21978039)the Natural Science Foundation of Jiangsu Province(BK20221265,BK20211100)the Fundamental Research Funds for the Central Universities(DUT21YG133,DUT22YG224)。
文摘Polymers with metal coordination ability are outstanding precursors of nanocatalysts,attracting numerous attention in nanocatalysis area.It has been rarely reported for the poly(N-sulfonyl amidines)as macromolecular ligands for nanocatalysis.Herein,a catalyst-free multicomponent polymerization(MCP)strategy is developed to facilely prepare a library of amphiphilic poly(Nsulfonyl amidines)with zwitterionic properties starting from disulfonyl azide,hydrophilic dialdehyde and cyclic amino acids including proline and pipecolinic acid.Metals or additives can be thorougly avoided through this method.All the obtained polymers have well-defined structures,high yields and weight-average molecular weights(M_(w)s,up to 99,300 g/mol).The unique zwitterionic property,amphiphilicity and Cu(Ⅰ)coordination ability of the obtained poly(N-sulfonyl amidines)endow them to form the polymer-Cu(Ⅰ)complexes as nanocatalysts.Such nanocatalysts exhibit high catalytic efficiency in aqueous Cucatalyzed azide-alkyne cycloaddition(CuAAC)reaction at a low Cu(Ⅰ)loading of 50 ppm.Nanocatalysts with a high ratio of polymers to Cu(Ⅰ)have also been demonstrated with Cu(Ⅰ)stabilization ability.This work provides a“green”MCP method toward zwitterionic and amphiphilic poly(N-sulfonyl amidines),and highlights their unique potentials for nanocatalysis.