Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is cr...Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is crucial for revealing the typical surface restructuring and catalyst dissolution during electrocatalysis.Although advanced in situ tools and theoretical models have been proposed[1,2],identifying the nature of the active sites with atomic-scale spatial resolution remains a challenge,especially at ESLIs.In a recent work published in Nature,Zhang et al.[3]reported a groundbreaking atomic-resolution imaging of the structural dynamics of Cu nanowire catalysts in ESLIs for electrochemical CO_(2)reduction(ECR).展开更多
The hydrogen evolution reaction(HER) through electrocatalysis is promising for the production of clean hydrogen fuel. However,designing the structure of catalysts,controlling their electronic properties,and manipulati...The hydrogen evolution reaction(HER) through electrocatalysis is promising for the production of clean hydrogen fuel. However,designing the structure of catalysts,controlling their electronic properties,and manipulating their catalytic sites are a significant challenge in this field. Here,we propose an electrochemical surface restructuring strategy to design synergistically interactive phosphorus-doped carbon@MoP electrocatalysts for the HER. A simple electrochemical cycling method is developed to tune the thickness of the carbon layers that cover on MoP core,which significantly influences HER performance. Experimental investigations and theoretical calculations indicate that the inactive surface carbon layers can be removed through electrochemical cycling,leading to a close bond between the MoP and a few layers of coated graphene. The electronsdonated by the MoP core enhance the adhesion and electronegativity of the carbon layers;the negatively charged carbon layers act as an active surface. The electrochemically induced optimization of the surface/interface electronic structures in the electrocatalysts significantly promotes the HER. Using this strategy endows the catalyst with excellent activity in terms of the HER in both acidic and alkaline environments(current density of 10 mA cm^(-2) at low overpotentials,of 68 mV in 0.5 M H_(2)SO_(4) and 67 mV in 1.0 M KOH).展开更多
The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reductio...The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reduction to methanol.In situ and quasi-operando spectroscopic results provide a deep insight into the catalytic active centres of reconstructed heterogeneous catalysts for CO_(2) electroreduction.展开更多
The surface stability of coinage metals is paramount when they are used as electrode materials for functional electronic devices incorporating organic semiconductors. In this work, it is shown that the adsorption of n...The surface stability of coinage metals is paramount when they are used as electrode materials for functional electronic devices incorporating organic semiconductors. In this work, it is shown that the adsorption of non-planar vanadyl phthalocyanine molecules on Cu（110） drastically restructured the metal surface at room temperature, which was further enhanced upon moderate annealing. Scanning tunneling microscopy imaging demonstrated that the surface was restructured at step edges into sawtooth features that gradually replaced the （110） terraces. The edges of the modified steps were preferentially composed of chiral （1×6） kink sites decorated with vanadyl phthalocyanine molecules adsorbed in a tilted configuration with the oxygen atom pointing downwards. These results can have a strong impact on the optimization of the performance of organic devices integrated with phthalocyanine molecules.展开更多
Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential dep...Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.展开更多
Identification of the catalytic dynamics and plasmonic effects plays a critical role in the design of heterogeneous catalysts.However,the knowledge of plasmonic effect on catalytic dynamics remains limited at the sing...Identification of the catalytic dynamics and plasmonic effects plays a critical role in the design of heterogeneous catalysts.However,the knowledge of plasmonic effect on catalytic dynamics remains limited at the single-particle level.Using the non-fluorescent amplex red to fluorescent resorufin as a model reaction,significant enhancement in catalytic efficiency from the coupled Au nanocube dimer(AuCD)was clearly revealed with the single-molecule fluorescence microscopy.AuCD exhibits noticeably higher catalytic efficiency than the monomer,which is attributed to the spontaneous dynamic surface restructuring.Spatiotemporally resolved dynamics suggest that the active catalytic sites essentially originate from the plasmonic nanogap where an electromagnetic(EM)hot spot exists.The enhanced EM field accelerates the generation of hot carriers and promotes the spontaneous surface restructuring by enhancing the lattice vibrations,which ultimately improves the catalytic activity.These microscopic views provide new insights into the effect of EM fields on surface restructuring dynamics of nanocatalysts.展开更多
Polypropylene （PP） was treated by an oxygen capacitively coupled radio frequency plasma （CCP） under a radio frequency （RF） power of 200 W for exposure time of 1, 5, and 10 rain. The ageing process of the plasma-...Polypropylene （PP） was treated by an oxygen capacitively coupled radio frequency plasma （CCP） under a radio frequency （RF） power of 200 W for exposure time of 1, 5, and 10 rain. The ageing process of the plasma- treated PP was studied at an ageing temperature of 90 ~C during an ageing time up to 25 h. The formation of the nanotextures with different geometry and aspect ratio and the grafting of large number of oxygen- containing groups were achieved on as-treated PP surfaces under the oxygen CCP treatment for the increased exposure time. The hydrophilicity on the as-treated PP surfaces with the stable nanotextures was rapidly depressed during the ageing process at 90 ℃ due to the restructuring of chemical composition. The surface restructuring rate was dependent on the aspect ratio and the oxygen-containing groups on the nanotextured PP with increasing exposure time. The hydrophobic over-recovery to high hydrophobicity and superhydrophobicity were observed on the post-aged surfaces with the stable nanofibrils from as-treated hydrophilic surfaces. The superhydrophobicity with the low water adhesion was achieved on the post-aged surfaces preserving the nanofibrils with high aspect ratio and large distance due to the decrease of the oxygen-containing groups after the surface restructuring.展开更多
The pressing challenges of the energy crisis and environmental problems necessitate the pursuit of efficient and sustainable energy conversion technologies,wherein catalytic processes play a vital role in addressing t...The pressing challenges of the energy crisis and environmental problems necessitate the pursuit of efficient and sustainable energy conversion technologies,wherein catalytic processes play a vital role in addressing these issues.Single-molecule fluorescence microscopy(SMFM)offers a transformative approach to understanding various catalytic reactions by enabling real-time visualization of molecular adsorption,diffusion,and transformation on catalytic surfaces.The unprecedented insights into the spatial distribution of active sites,catalytic heterogeneity,and the dynamics of key intermediates result in single-or subparticle level structure−property relations,thereby offering insightful perspectives for catalyst design and mechanistic understanding of energy-related catalytic processes.In this review,we provide an overview of the recent progress in using SMFM for investigating energy-related catalytic reactions.The advancement in SMFM imaging techniques for investigating nonfluorescent chemical processes is also highlighted.Finally,we conclude the review by commenting on the current challenges and prospects in advancing SMFM in energy research.We hope that the capable SMFM imaging techniques and insights will promote the development and realistic application of various energy-related catalytic reactions,together with inspiring researchers to explore the power of SMFM in other applications.展开更多
基金financially supported by the Natural Science Foundation of Shandong(ZR2023ME014)。
文摘Electrocatalysis has been extensively explored for the storage and conversion of renewable electric power.Understanding the physisorption and chemisorption processes at electrified solid–liquid interfaces(ESLIs)is crucial for revealing the typical surface restructuring and catalyst dissolution during electrocatalysis.Although advanced in situ tools and theoretical models have been proposed[1,2],identifying the nature of the active sites with atomic-scale spatial resolution remains a challenge,especially at ESLIs.In a recent work published in Nature,Zhang et al.[3]reported a groundbreaking atomic-resolution imaging of the structural dynamics of Cu nanowire catalysts in ESLIs for electrochemical CO_(2)reduction(ECR).
基金supported by the National Natural Science Foundation of China (Grant Nos. 21975286 and 21473254)the Special Project Fund of “Taishan Scholar” of Shandong Province (Grant No. ts201511017)+2 种基金the QLUT Special Funding for Distinguished Scholars (Grant No. 2419010420)the project ZR2020QE058 supported by Shandong Provincial Natural Science Foundationthe Fundamental Research Funds for the Central Universities (Grant Nos. YCX2020050,18CX06030A,and 17CX02039A)。
文摘The hydrogen evolution reaction(HER) through electrocatalysis is promising for the production of clean hydrogen fuel. However,designing the structure of catalysts,controlling their electronic properties,and manipulating their catalytic sites are a significant challenge in this field. Here,we propose an electrochemical surface restructuring strategy to design synergistically interactive phosphorus-doped carbon@MoP electrocatalysts for the HER. A simple electrochemical cycling method is developed to tune the thickness of the carbon layers that cover on MoP core,which significantly influences HER performance. Experimental investigations and theoretical calculations indicate that the inactive surface carbon layers can be removed through electrochemical cycling,leading to a close bond between the MoP and a few layers of coated graphene. The electronsdonated by the MoP core enhance the adhesion and electronegativity of the carbon layers;the negatively charged carbon layers act as an active surface. The electrochemically induced optimization of the surface/interface electronic structures in the electrocatalysts significantly promotes the HER. Using this strategy endows the catalyst with excellent activity in terms of the HER in both acidic and alkaline environments(current density of 10 mA cm^(-2) at low overpotentials,of 68 mV in 0.5 M H_(2)SO_(4) and 67 mV in 1.0 M KOH).
基金supported by the National Natural Science Foundation of China(51771072)the Outstanding Youth Scientist Foundation of Hunan Province(2020JJ2006)+2 种基金the Youth 1000 Talent Program of ChinaFundamental Research Funds for the Central UniversitiesHunan University State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body Independent Research Project(71860007)。
文摘The nanoporous Cu_(2-x)Se with Cu(Se-5%)surface catalysts were prepared through in situ dynamic restructuring strategy during the electrochemical process,which achieves highly selective electrochemical CO_(2) reduction to methanol.In situ and quasi-operando spectroscopic results provide a deep insight into the catalytic active centres of reconstructed heterogeneous catalysts for CO_(2) electroreduction.
文摘The surface stability of coinage metals is paramount when they are used as electrode materials for functional electronic devices incorporating organic semiconductors. In this work, it is shown that the adsorption of non-planar vanadyl phthalocyanine molecules on Cu（110） drastically restructured the metal surface at room temperature, which was further enhanced upon moderate annealing. Scanning tunneling microscopy imaging demonstrated that the surface was restructured at step edges into sawtooth features that gradually replaced the （110） terraces. The edges of the modified steps were preferentially composed of chiral （1×6） kink sites decorated with vanadyl phthalocyanine molecules adsorbed in a tilted configuration with the oxygen atom pointing downwards. These results can have a strong impact on the optimization of the performance of organic devices integrated with phthalocyanine molecules.
文摘Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.
基金This research was made possible by a generous grant from National Natural Science Foundation of China(NSFC,project no.21974073).
文摘Identification of the catalytic dynamics and plasmonic effects plays a critical role in the design of heterogeneous catalysts.However,the knowledge of plasmonic effect on catalytic dynamics remains limited at the single-particle level.Using the non-fluorescent amplex red to fluorescent resorufin as a model reaction,significant enhancement in catalytic efficiency from the coupled Au nanocube dimer(AuCD)was clearly revealed with the single-molecule fluorescence microscopy.AuCD exhibits noticeably higher catalytic efficiency than the monomer,which is attributed to the spontaneous dynamic surface restructuring.Spatiotemporally resolved dynamics suggest that the active catalytic sites essentially originate from the plasmonic nanogap where an electromagnetic(EM)hot spot exists.The enhanced EM field accelerates the generation of hot carriers and promotes the spontaneous surface restructuring by enhancing the lattice vibrations,which ultimately improves the catalytic activity.These microscopic views provide new insights into the effect of EM fields on surface restructuring dynamics of nanocatalysts.
基金supported by the projects supported by the National Natural Science Foundation of China(Nos.51005032 and 51321004)
文摘Polypropylene （PP） was treated by an oxygen capacitively coupled radio frequency plasma （CCP） under a radio frequency （RF） power of 200 W for exposure time of 1, 5, and 10 rain. The ageing process of the plasma- treated PP was studied at an ageing temperature of 90 ~C during an ageing time up to 25 h. The formation of the nanotextures with different geometry and aspect ratio and the grafting of large number of oxygen- containing groups were achieved on as-treated PP surfaces under the oxygen CCP treatment for the increased exposure time. The hydrophilicity on the as-treated PP surfaces with the stable nanotextures was rapidly depressed during the ageing process at 90 ℃ due to the restructuring of chemical composition. The surface restructuring rate was dependent on the aspect ratio and the oxygen-containing groups on the nanotextured PP with increasing exposure time. The hydrophobic over-recovery to high hydrophobicity and superhydrophobicity were observed on the post-aged surfaces with the stable nanofibrils from as-treated hydrophilic surfaces. The superhydrophobicity with the low water adhesion was achieved on the post-aged surfaces preserving the nanofibrils with high aspect ratio and large distance due to the decrease of the oxygen-containing groups after the surface restructuring.
基金support by the National University of Singapore start-up grant,Centre for Hydrogen Innovations(grant no.CHI-P2023-04)National Research Foundation of Singapore(grant No.U2411D4005)+2 种基金Ministry of Education(grant no.23-0646-A0001 and T2EP50124-0006)the National Research Foundation(grant no.24-1637-A0004)Prime Minister’s Office,Singapore under its Campus for Research Excellence and Technological Enterprise(CREATE)programme(Development of advanced catalysts for electrochemical carbon abatement).
文摘The pressing challenges of the energy crisis and environmental problems necessitate the pursuit of efficient and sustainable energy conversion technologies,wherein catalytic processes play a vital role in addressing these issues.Single-molecule fluorescence microscopy(SMFM)offers a transformative approach to understanding various catalytic reactions by enabling real-time visualization of molecular adsorption,diffusion,and transformation on catalytic surfaces.The unprecedented insights into the spatial distribution of active sites,catalytic heterogeneity,and the dynamics of key intermediates result in single-or subparticle level structure−property relations,thereby offering insightful perspectives for catalyst design and mechanistic understanding of energy-related catalytic processes.In this review,we provide an overview of the recent progress in using SMFM for investigating energy-related catalytic reactions.The advancement in SMFM imaging techniques for investigating nonfluorescent chemical processes is also highlighted.Finally,we conclude the review by commenting on the current challenges and prospects in advancing SMFM in energy research.We hope that the capable SMFM imaging techniques and insights will promote the development and realistic application of various energy-related catalytic reactions,together with inspiring researchers to explore the power of SMFM in other applications.
