Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-ar...Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1).The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.展开更多
Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the...Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the molecular harmonic spectrum provide crucial insights into the structural or multielectron dynamical effects induced by intense laser fields. In this study, we measure the high-order harmonic spectrum of aligned CO_(2) molecules contributed from short trajectories. Two distinct groups of minima are identified in the plateau region. Our findings indicate that the deeper-lying molecular orbitals and two-center interference play significant roles in molecular harmonic generation. The results pave the way for advancing the understanding of multielectron dynamics in polyatomic molecules under intense laser fields.展开更多
The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristi...The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.展开更多
Currently,simultaneous regulation of external morphology and internal electronic structure for Na_(3)V_(2)(PO_(4))_(3)(NVP)is rarely realized.Herein,complexes of β-cyclodextrin(βCD)and ethylenediaminetetraacetic aci...Currently,simultaneous regulation of external morphology and internal electronic structure for Na_(3)V_(2)(PO_(4))_(3)(NVP)is rarely realized.Herein,complexes of β-cyclodextrin(βCD)and ethylenediaminetetraacetic acid ferric sodium salt(EDTAFeNa)are utilized for the one-step preparation of NVP with spherical morphology as well as Fe substitution.βCD is initially hydrolyzed into glucose,and then carbon microspheres with numerous pores are formed through continuous dehydration and carbonization.The intermediate hydroxymethylfurfural is rich in active functional groups,which are attractive for the V/P-contained raw materials.Accordingly,the nucleation sites for NVP are successfully limited in the spherical framework,possessing a superior surface area of 97.15 g m^(-2).Furthermore,the beneficial Fe in EDTAFeNa enters into the NVP bulk to construct a novel Fe-doped Na_(3)V_(1.95)Fe_(0.05)(PO_(4))_(3)(NVP/β-ISC)material.Fe-substitution induces significant optimizations of electronic structure for NVP,which has been verified by the newly generated abundant oxygen vacancies and extended V-O bond length.Moreover,a multielectron reaction is activated,resulting from the V^(4+)/V^(5+)redox couple.The charge compensation mechanism of NVP/β-ISC is also deeply investigated.Density functional theory(DFT)calculations theoretically elaborate the mechanism of Fe-doping.Consequently,NVP/β-ISC reveals superior sodium storage performance in both half and full cells and even at different extreme conditions(needling,soaking,bending,and freezing).展开更多
Cross sections of electron-loss in H（1s）＋ H（1s） collisions and total collisional destruction of H（2s） in H（1s） 4- H（2s） collisions are calculatted by four-body classical-trajectory Monte Caylo （CTMC） meth...Cross sections of electron-loss in H（1s）＋ H（1s） collisions and total collisional destruction of H（2s） in H（1s） 4- H（2s） collisions are calculatted by four-body classical-trajectory Monte Caylo （CTMC） method and compared with previous theoretical and experimental data over the energy range of 4-100 keV. For the former a good agreement is obtained within different four-body CTMC calculations, and for the incident energy Ep 〉 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approx- imation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H（2p）, single- and double-ionization and H- formation in H（2s）＋H（2s） collisions are calculated in the energy range of 4-100 keV for the first time, and compared with those in H（1s）＋H（1s） and H（1s）＋U（2s） collisions.展开更多
The field-ionization Coulomb explosion model is extended to investigate the multielectron dissociative ionization process of N2 molecule irradiated by an intense femtosecond laser field with an arbitrary polarization....The field-ionization Coulomb explosion model is extended to investigate the multielectron dissociative ionization process of N2 molecule irradiated by an intense femtosecond laser field with an arbitrary polarization. The ionization process of N2 molecule is found to be optimal at the critical internuclear distance Rc=7a.u., which is independent of the laser polarization state, the molecular explosion channel and the angle between the molecular axis and the direction of laser electric field. The kinetic energies of the ion fragments are identical in the cases of linear and circular polarizations at the same incident laser intensity. However, the probability of electron ionization is very sensitive to the above three parameters. At the critical distance Rc=7a.u. the angular dependence of the threshold intensity for the over-the-barrier ionization leads to the geometric alignment of molecules in the case of linear polarization. The threshold intensity in the case of circular polarization is apparently higher than that in the case of linear polarization, which can well explain the significant decrease of ionization in the case of circular polarization. The numerical calculations are compared with the experimental measurements.展开更多
Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by...Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.展开更多
CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion req...CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction(toward water splitting systems).Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology.Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting,semiconducting,and insulating and diverse catalytic properties at their surface depending on the exposing facet,as well as physical and chemical robustness under ambient conditions.We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors.We have developed an easy preparation technique of mono-and multimetallic oxide films,termed the“mixed metal-imidazole casting(MiMIC)method”,by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand,followed by calcination.The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions,because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films.In this Account,we expound synthesis and characterization of a variety of mono-and multimetallic oxide films using the MiMIC method and its application to electro-and photoelectrocatalysis for water splitting and oxygen reduction,which are important key reactions in future sustainable technology.The adherability of these films onto the electrode surface is prominent although their morphology,crystallinity,and nanostructures depend on the metal oxide materials,which is one of the important factors to induce high performance of the metal oxide films for electro-and photoelectrocatalysis.Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice,and a structure-directing agent for the anisotropic crystallization,as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate.These findings surely expand material development to a great extent,by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR)to produce value‐added products has received tremendous research attention in recent years.With research efforts across the globe,remarkable advancement has been ach...Electrochemical CO_(2) reduction reaction(CO_(2)RR)to produce value‐added products has received tremendous research attention in recent years.With research efforts across the globe,remarkable advancement has been achieved,including the improvement of selectivity for the reduction products,the realization of efficient reduction beyond two electrons,and the delivery of industrially relevant current densities.In this review,we introduce the recent development of nanomaterials for CO_(2)RR,including the zero‐dimensional graphene quantum dots,two‐dimensional materials such as metal chalcogenides and metal/covalent organic framework,singleatom catalysts,and nanostructured metal catalysts.The engineering of materials into three‐dimensional structure will also be discussed.Finally,we will provide a summary of the catalytic performance and perspectives on future development.展开更多
Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumpt...Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumption worldwide.However,complicated sul-fur redox reactions and polysulfide shuttling signifi-cantly postpone the applications of lithium-sulfur batteries with rapid capacity decay and low Coulom-bic efficiency.展开更多
Plasmonic hot electrons have long been regarded as a promising energy source for inducing chemical transformations.However,because of the mismatch between the electron cloud of reactant molecules and the hot-electron ...Plasmonic hot electrons have long been regarded as a promising energy source for inducing chemical transformations.However,because of the mismatch between the electron cloud of reactant molecules and the hot-electron gas of metal nanoparticles(NPs),the highly localized and short-lived hot electrons are dif-ficult to utilize in bulk synthesis when the reactant molecules do not have a strong affinity for the metal surface.Here,we propose the concept of polarized nanocatalysts to mimic chemical polarity at the nanometer scale.Under plasmonic photorecycling conditions,the rationally designed asymmetric Ag-TiO_(2) hybrid NPs enable six-electron reduction of molecules in bulk solution.This hot-electron-driven reaction does not require a conventional hydrogen or hydride reducing agent.As a proof-of-concept,one-pot photocatalytic syntheses of amides,such as paracetamol,using nitro reactants were performed.This provides a new opportunity to enable challenging multielectron transformations in organic chemistry.展开更多
基金partly supported by the National Natural Science Foundation of China(No.22301108)the Project Startup Foundation for Distinguished Scholars of Jiangsu University(Nos.4111310026 and 5501310014).
文摘Novel benzo-bridged hexaphyrin(2.1.2.1.2.1)and its copper complex were synthesized.Single-crystal structures showed typical figure-of-eight Huckel topologies.NMR,NICS,HOMA,ACID,and EDDB analysis supported their non-aromatic properties owning to the strong local aromatic benzo rings cutting the global aromatic ring of the benzo-bridged figure-of-eight hexaphyrin(2.1.2.1.2.1).The redox properties and degenerate HOMOs and LUMOs levels indicate multielectron donating and accepting abilities.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 92250306 and 12304302)the Natural Science Foundation of Jilin Province, China (Grant Nos. YDZJ202101ZYTS157 and YDZJ202201ZYTS314)the Scientific Research Foundation of Jilin Province Education Department, China (Grant No. JJKH20230283KJ)。
文摘Molecular high-order harmonic spectroscopy is a significant advancement in ultrafast science, enabling the measurement of multielectron dynamics with attosecond temporal resolution. The fine structures observed in the molecular harmonic spectrum provide crucial insights into the structural or multielectron dynamical effects induced by intense laser fields. In this study, we measure the high-order harmonic spectrum of aligned CO_(2) molecules contributed from short trajectories. Two distinct groups of minima are identified in the plateau region. Our findings indicate that the deeper-lying molecular orbitals and two-center interference play significant roles in molecular harmonic generation. The results pave the way for advancing the understanding of multielectron dynamics in polyatomic molecules under intense laser fields.
基金supported by the NSFC under Grant Nos.11374315 and 12074395the Invited Scientist Program of CNRS at Ecole Polytechnique,Palaiseau,France。
文摘The capacity to predict X-ray transition and K-edge energies in dense finite-temperatur plasmas with high precision is of primary importance for atomic physics of matter under extreme conditions.The dual characteristics of bound and continuum states in dense matter are modeled by a valence-band-like structure in a generalized ion-sphere approach with states that are either bound,free,or mixed.The self-consistent combination of this model with the Dirac wave equations of multielectron bound states allows one to fully respect the Pauli principle and to take into account the exact nonlocal exchange terms.The generalized method allows very high precision without implication of calibration shifts and scaling parameters and therefore has predictive power.This leads to new insights in the analysis of various data.The simple ionization model representing the K-edge is generalized to excitation–ionization phenomena resulting in an advanced interpretation of ionization depression data in near-solid-density plasmas.The model predicts scaling relations along the isoelectronic sequences and the existence of bound M-states that are in excellent agreement with experimental data,whereas other methods have failed.The application to unexplained data from compound materials also gives good agreement without the need to invoke any additional assumptions in the generalized model,whereas other methods have lacked consistency.
基金financially supported by the Key Research and Development(R&D)Projects of Shanxi Province(202202040201005)the Graduate Innovation Project of Shanxi Province(No.2024SJ261)。
文摘Currently,simultaneous regulation of external morphology and internal electronic structure for Na_(3)V_(2)(PO_(4))_(3)(NVP)is rarely realized.Herein,complexes of β-cyclodextrin(βCD)and ethylenediaminetetraacetic acid ferric sodium salt(EDTAFeNa)are utilized for the one-step preparation of NVP with spherical morphology as well as Fe substitution.βCD is initially hydrolyzed into glucose,and then carbon microspheres with numerous pores are formed through continuous dehydration and carbonization.The intermediate hydroxymethylfurfural is rich in active functional groups,which are attractive for the V/P-contained raw materials.Accordingly,the nucleation sites for NVP are successfully limited in the spherical framework,possessing a superior surface area of 97.15 g m^(-2).Furthermore,the beneficial Fe in EDTAFeNa enters into the NVP bulk to construct a novel Fe-doped Na_(3)V_(1.95)Fe_(0.05)(PO_(4))_(3)(NVP/β-ISC)material.Fe-substitution induces significant optimizations of electronic structure for NVP,which has been verified by the newly generated abundant oxygen vacancies and extended V-O bond length.Moreover,a multielectron reaction is activated,resulting from the V^(4+)/V^(5+)redox couple.The charge compensation mechanism of NVP/β-ISC is also deeply investigated.Density functional theory(DFT)calculations theoretically elaborate the mechanism of Fe-doping.Consequently,NVP/β-ISC reveals superior sodium storage performance in both half and full cells and even at different extreme conditions(needling,soaking,bending,and freezing).
基金Supported by the National Natural Science Foundation of China under Grant Nos 10434100, 10574018 and 10574020.
文摘Cross sections of electron-loss in H（1s）＋ H（1s） collisions and total collisional destruction of H（2s） in H（1s） 4- H（2s） collisions are calculatted by four-body classical-trajectory Monte Caylo （CTMC） method and compared with previous theoretical and experimental data over the energy range of 4-100 keV. For the former a good agreement is obtained within different four-body CTMC calculations, and for the incident energy Ep 〉 10 keV, comparison with the experimental data shows a better agreement than the results calculated by the impact parameter approx- imation. For the latter, our theory predicts the correct experimental behaviour, and the discrepancies between our results and experimental ones are less than 30%. Based on the successive comparison with experiments, the cross sections for excitation to H（2p）, single- and double-ionization and H- formation in H（2s）＋H（2s） collisions are calculated in the energy range of 4-100 keV for the first time, and compared with those in H（1s）＋H（1s） and H（1s）＋U（2s） collisions.
基金Project supported by the National Key Basic Research Special Foundation （NKBRSF） （Grant No TG1999075207） and the National Natural Science Foundation of China （Grant Nos 10104003, 90206003 and 60378012） and the China Postdoctoral Science Foundation （Grant No 2003034093）.
文摘The field-ionization Coulomb explosion model is extended to investigate the multielectron dissociative ionization process of N2 molecule irradiated by an intense femtosecond laser field with an arbitrary polarization. The ionization process of N2 molecule is found to be optimal at the critical internuclear distance Rc=7a.u., which is independent of the laser polarization state, the molecular explosion channel and the angle between the molecular axis and the direction of laser electric field. The kinetic energies of the ion fragments are identical in the cases of linear and circular polarizations at the same incident laser intensity. However, the probability of electron ionization is very sensitive to the above three parameters. At the critical distance Rc=7a.u. the angular dependence of the threshold intensity for the over-the-barrier ionization leads to the geometric alignment of molecules in the case of linear polarization. The threshold intensity in the case of circular polarization is apparently higher than that in the case of linear polarization, which can well explain the significant decrease of ionization in the case of circular polarization. The numerical calculations are compared with the experimental measurements.
基金supported by the National Natural Science Foundation of China(52072118,51772089)the Youth 1000 Talent Program of China+3 种基金the Research and Development Plan of Key Areas in Hunan Province(2019GK2235)the Key Research and Development Program of Ningxia(2020BDE03007)the China Postdoctoral Science Foundation(2019M653649)the Guangdong Basic and Applied Basic Research Fund(2019A1515110518,2019A1515111188,2020B0909030004)。
文摘Developing suitable anode materials for potassium-ion batteries(PIBs)remains a great challenge owing to the limited theoretical capacity of active materials and large radius of K+ion(1.38?).To solve these obstacles,by integrating the principles of multielectron transfer and rational porous crystal framework,we creatively propose the monoclinic Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O(CVO)as a novel anode for PIBs.Furthermore,inspired by the metastable nature of CVO under high temperature/pressure,we skillfully design a facile hydrothermal recrystallization strategy without the phase change and surfactants addition.Thus,for the first time,the porous composite of Cu_(3)(OH)_(2)V_(2)O_(7)·2H_(2)O nanobelts covered in situ by reduced graphene oxide(CVO NBs/r GO)was assembled,greatly improving the deficiencies of CVO.When used as a novel anode for PIBs,CVO NBs/r GO delivers large specific capacity(up to 551.4 m Ah g^(-1)at 50 m A g^(-1)),high-rate capability(215.3 m Ah g^(-1)at 2.5 A g^(-1))and super durability(203.6 m Ah g^(-1)at 500 m A g^(-1)even after 1000 cycles).The outstanding performance can be ascribed to the synergistic merits of desirable structural features of monoclinic CVO nanobelts and the highly conductive graphene 3D network,thus promoting the composite material stability and electrical/ionic conductivity.This work reveals a novel metal vanadate-based anode material for PIBs,would further motivate the subsequent batteries research on M_(3)(OH)_(2)V_(2)O_(7)-n H_(2)O(M;Co,Ni,Cu,Zn),and ultimately expands valuable fundamental understanding on designing other high-performance electrode materials,including the combined strategies of multielectron transfer with rational porous crystal framework,and the composite fabrication of 1D electrode nanostructure with conductive carbon matrix.
基金supported by JSPS KAKENHI Grant Numbers JP21H02042,JP22K18309,and JP22K14762.
文摘CONSPECTUS:Electrochemical and photoelectrochemical conversion of renewable energy sources into useful chemicals and fuels is of paramount importance for future sustainable technologies.Renewable energy conversion requires catalysts for multielectron redox reactions such as water oxidation and reduction(toward water splitting systems).Developing efficient catalysts for multielectron redox reactions is a great challenge in current science and technology.Metal oxides have been extensively researched to be applied to a large variety of photonic and electronic devices due to the wide range of electronic properties of conducting,semiconducting,and insulating and diverse catalytic properties at their surface depending on the exposing facet,as well as physical and chemical robustness under ambient conditions.We aspire to the development of an easy technique available for large-scale production of metal oxide films based on simple casting and calcination to adopt a strategy for controlling the formation and growth of metal oxide films by ligands to metal centers in precursors.We have developed an easy preparation technique of mono-and multimetallic oxide films,termed the“mixed metal-imidazole casting(MiMIC)method”,by which metal oxide films are generated tightly on various electrode substrates by casting precursor solutions or suspensions containing component metal salts in a mixed solvent of methanol/imidazole derivative as a ligand,followed by calcination.The general versatility of the MiMIC method encourages us to hunt new metal oxide films as efficient catalysts for the multielectron redox reactions,because the rigid adherability of films formed on a current collector electrode is necessary for essential evaluation of the catalytic performance of the metal oxide films.In this Account,we expound synthesis and characterization of a variety of mono-and multimetallic oxide films using the MiMIC method and its application to electro-and photoelectrocatalysis for water splitting and oxygen reduction,which are important key reactions in future sustainable technology.The adherability of these films onto the electrode surface is prominent although their morphology,crystallinity,and nanostructures depend on the metal oxide materials,which is one of the important factors to induce high performance of the metal oxide films for electro-and photoelectrocatalysis.Imidazole derivatives were found to act as a source of nitrogen for the N-doping to a metal oxide lattice,and a structure-directing agent for the anisotropic crystallization,as well as a binder among constituting nanoparticles to lead to the rigid adherability of films on the substrate.These findings surely expand material development to a great extent,by not only changing the metal compositions but also being based on band engineering due to doping of representative elements and crystal facet control of metal oxide films.
基金Research Grants Council,University Grants Committee,Grant/Award Number:21300620Guangdong Basic and Applied Basic Research Fund。
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR)to produce value‐added products has received tremendous research attention in recent years.With research efforts across the globe,remarkable advancement has been achieved,including the improvement of selectivity for the reduction products,the realization of efficient reduction beyond two electrons,and the delivery of industrially relevant current densities.In this review,we introduce the recent development of nanomaterials for CO_(2)RR,including the zero‐dimensional graphene quantum dots,two‐dimensional materials such as metal chalcogenides and metal/covalent organic framework,singleatom catalysts,and nanostructured metal catalysts.The engineering of materials into three‐dimensional structure will also be discussed.Finally,we will provide a summary of the catalytic performance and perspectives on future development.
基金This work was supported by National Key Re-search and Development Program(2016YFA0202500,2015CB932500,and2016YFA0200102)National Natural Scientific Foundation of China(21676160 and 21825501)Tsinghua University Initiative Scientific Research Program.
文摘Lithium–sulfur batteries with an ultrahigh theoretical energy density of 2600 Wh kg^(−1) are highly consid-ered as desirable next-generation energy storage devices that will meet the growing demand of energy consumption worldwide.However,complicated sul-fur redox reactions and polysulfide shuttling signifi-cantly postpone the applications of lithium-sulfur batteries with rapid capacity decay and low Coulom-bic efficiency.
基金financial support from the National Key R&D Program of China(grant no.2021YFB4000600)the National Natural Science Foundation of China(grant no.22022406)+2 种基金the Natural Science Foundation of Tianjin(grant nos.20JCJQJC00110 and 20JCYBJC00590)the 111 project(grant no.B12015)the Haihe Laboratory of Sustainable Chemical Transformations.
文摘Plasmonic hot electrons have long been regarded as a promising energy source for inducing chemical transformations.However,because of the mismatch between the electron cloud of reactant molecules and the hot-electron gas of metal nanoparticles(NPs),the highly localized and short-lived hot electrons are dif-ficult to utilize in bulk synthesis when the reactant molecules do not have a strong affinity for the metal surface.Here,we propose the concept of polarized nanocatalysts to mimic chemical polarity at the nanometer scale.Under plasmonic photorecycling conditions,the rationally designed asymmetric Ag-TiO_(2) hybrid NPs enable six-electron reduction of molecules in bulk solution.This hot-electron-driven reaction does not require a conventional hydrogen or hydride reducing agent.As a proof-of-concept,one-pot photocatalytic syntheses of amides,such as paracetamol,using nitro reactants were performed.This provides a new opportunity to enable challenging multielectron transformations in organic chemistry.
