By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variationa...By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-vip electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.展开更多
Aqueous zinc-ion batteries(ZIBs)have shown great potential in the fields of wearable devices,consumer electronics,and electric vehicles due to their high level of safety,low cost,and multiple electron transfer.The lay...Aqueous zinc-ion batteries(ZIBs)have shown great potential in the fields of wearable devices,consumer electronics,and electric vehicles due to their high level of safety,low cost,and multiple electron transfer.The layered cathode materials of ZIBs hold a stable structure during charge and discharge reactions owing to the ultrafast and straightforward(de)intercalation-type storage mechanism of Zn^(2+)ions in their tunable interlayer spacing and their abilities to accommodate other vip ions or molecules.Nevertheless,the challenges of inadequate energy density,dissolution of active materials,uncontrollable byproducts,increased internal pressure,and a large de-solvation penalty have been deemed an obstacle to the development of ZIBs.In this review,recent strategies on the structure regulation of layered materials for aqueous zinc-ion energy storage devices are systematically summarized.Finally,critical science challenges and future outlooks are proposed to guide and promote the development of advanced cathode materials for ZIBs.展开更多
The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric ene...The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.展开更多
Benefiting from the ultrahigh specific surface areas,highly accessible surface atoms,and highly tunable microscopic structures,the two-dimensional metallenes as nanocatalysts have displayed promising performance for v...Benefiting from the ultrahigh specific surface areas,highly accessible surface atoms,and highly tunable microscopic structures,the two-dimensional metallenes as nanocatalysts have displayed promising performance for various electrocatalytic reactions.Herein,we reviewed recent advances on metallenes in structural regulations including defect,phase,strain,interface,doping,and alloying engineering strategies and their applications in energy electrocatalytic reactions involving oxygen reduction reaction,carbon dioxide reduction reaction,hydrogen evolution reaction,and small molecules oxidation reaction.Finally,we proposed the future challenges and directions in this emerging area.展开更多
Based on the overall consideration of individual behaviors of Ricardian and non-Ricardian households, this paper develops a New Keynesian dynamic stochastic general equilibrium(DSGE) model to form a relatively systema...Based on the overall consideration of individual behaviors of Ricardian and non-Ricardian households, this paper develops a New Keynesian dynamic stochastic general equilibrium(DSGE) model to form a relatively systematic research framework for analyzing the economic effects of structural fiscal instruments. Our study findsthat great differences exist in the macroeconomic effects of different fiscal instruments, suggesting that the government should prudently select these fiscal instruments in fiscal macro-control. The simulating results of fiscal shocks show that the effect of tax cut is superior to the effect of increased spending. In the context of slowing economic growth and less potent stimulation policy, the government should transform its previous regulatory approach of fiscal policy and shift from hefty spending stimulus policy to structural tax cuts. This paper believes that China should step up the implementation of public-private partnership, increase its spending on social security, healthcare, pension and public services and facilitate the transition toward a service-based government; and that tax policy should focus on structural tax cuts on consumption to promote the transition of demand structure toward consumption-driven.展开更多
To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products hav...To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products have been gaining increasing interest.Cu-based CO_(2)reduction catalysts have attracted widespread attention owing to their capability of generating C1 and C_(2+)products.However,Cu-based catalysts are highly challenged by their low product selectivity.Recently,Cu-based bimetallic catalysts have been found the unique catalytical activity and selectivity in CO_(2)reduction reactions(CO_(2)RR).The incorporation of other metals can change the electronic circumstance of Cu-based catalysts,promoting the adsorption ability of the intermediate products and consequently leading to high selectivity.In this minireview,we intend to summarize recent advances of Cu-based bimetallic catalysts in producing C1 and C_(2+)products,involving designing heterostructure,alloy,defects and surface modification engineering.We pay special attention to the regulation of electronic structure of the composite catalysts,as well as insights into the relationship between electronic property and catalytical performance for Cu-based bimetallic catalysts.展开更多
The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with eq...The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.展开更多
Atomically dispersed catalysts(ADCs)have been diffusely researched for the development of advanced catalytic processes owing to their welldefined structure,high atomic utilization,and outstanding activity.Precisely de...Atomically dispersed catalysts(ADCs)have been diffusely researched for the development of advanced catalytic processes owing to their welldefined structure,high atomic utilization,and outstanding activity.Precisely decoding the intrinsic structures and coordination microenvironments of ADCs still confronts significant challenges.Overcoming these challenges is important for profound understanding of the structure-activity relationships and directing the future design of ADCs.Herein,this minireview summarizes recent progress and advanced characterization techniques for the engineering of ADCs,including single-atom catalysts,dualatom catalysts,and atomic cluster catalysts with regard to precise synthesis,structural regulation,and the structure-performance relationship.The catalytic merits and regulation strategies of recent breakthroughs in energy conversion,enzyme mimicry,and organic synthesis are thoroughly discussed to disclose the catalytic mechanism-guided ADCs design.Finally,a comprehensive summary of the future challenges and potential prospects is presented to stimulate more design and application possibilities for ADCs.We believe that this comprehensive minireview will open up novel pathways for the widespread utilization of ADCs in diverse catalytic processes.展开更多
At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficult...At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.展开更多
Sunlight-driven photocatalysis,which can produce clean fuels and mitigate environmental pollution,has received extensive research attention due to its potential for addressing both energy shortages and environmental c...Sunlight-driven photocatalysis,which can produce clean fuels and mitigate environmental pollution,has received extensive research attention due to its potential for addressing both energy shortages and environmental crises.Bismuth(Bi)-based photocatalysts with broad spectrum solar-light absorption and tunable structures,exhibit promising applications in solar-driven photocatalysis.Oxygen vacancy(OV)engineering is a widely recognized strategy that shows great potential for accelerating charge separation and small molecule activation.Based on OV engineering,this review focuses on Bi-based photocatalysts and provides a comprehensive overview including synthetic methods,regulation strategies,and applications in photocatalytic field.The synthetic methods of Bibased photocatalysts with OVs(BPOVs)are classified into hydrothermal,solvothermal,ultraviolet light reduction,calcination,chemical etching,and mechanical methods based on different reaction types,which provide the possibility for the structural regulation of BPOVs,including dimensional regulation,vacancy creation,elemental doping,and heterojunction fabrication.Furthermore,this review also highlights the photocatalytic applications of BPOVs,including CO_(2)reduction,N2 fixation,H2 generation,O_(2)evolution,pollutant degradation,cancer therapy,and bacteria inactivation.Finally,the conclusion and prospects toward the future development of BPOVs photocatalysts are presented.展开更多
The inherent electrocatalytic potential of transition metal phosphides(TMPs)for oxygen evolution is influenced by the reduced efficiency of electron transfer resulting from the interaction between electronegative phos...The inherent electrocatalytic potential of transition metal phosphides(TMPs)for oxygen evolution is influenced by the reduced efficiency of electron transfer resulting from the interaction between electronegative phosphorus atoms and transition metals.Here,we introduce Fe into Ni_(2)P nanocrystals by thermal injection synthesis method,and anchor them on nickel foam(NF)by facile spraying to prepare self-supporting oxygen evolution reaction(OER)electrocatalyst.Promisingly,the optimized electrode of Ni_(2)P-Fe-2/NF demonstrates low overpotentials of 212 mV with 10 mA·cm^(-2)and a 0.9%decay within300 h test of 50 mA·cm^(-2).Notably,when electrode size was expanded to 600 cm^(2)and applied to a larger electrolyzer,its 9 h decay rate at 6 A current was only 1.69%.Characterization results show that Fe doped NiOOH is generated during OER reaction as actual catalyst,Results from density functional theory(DFT)computations suggest that Fe doping shifts NiOOH d-band center to Fermi level,lowering critical *OOH intermediates formation energy barrier during the OER reaction.These findings inform the large-scale industrial application of TMPs as robust electrocatalysts.展开更多
The pursuit of highly efficient catalysts for the urea oxidation reaction(UOR)represents a pivotal and sustainable approach to the generation of renewable energy.Structural regulation has emerged as a particularly eff...The pursuit of highly efficient catalysts for the urea oxidation reaction(UOR)represents a pivotal and sustainable approach to the generation of renewable energy.Structural regulation has emerged as a particularly effective approach to achieving superior catalytic performance.However,in the realm of amorphous catalysts with disordered structure and remarkable catalytic potential,identifying effective regulation strategies to enhance the UOR performance remains a formidable yet critical challenge.In this study,we present a coupling modulation strategy based on the growth mode and pulse current,utilizing pulse electrodeposition(PED)to achieve amorphous Ni-P catalysts with high-efficiency UOR performance.Amorphous Ni/Ni-P catalyst engineered by Stranski-Krastanov(SK)growth mode along with low pulse current exhibits unprecedented catalytic activity for UOR,as evidenced by its overpotential of 1.35 V at 10 mA/cm^(2) and 1.37 V@100 mA/cm^(2).We reveal the regulation-relationship among the growth modes,catalyst structure and UOR performance by PED.We also show that low-pulse current can efficiently enhance UOR performance by elevating energy states in amorphous Ni-P,and further demonstrate the broad applicability across diverse growth modes.Therefore,by integrating film growth modes with a pulse current,we have established a novel method for significantly enhancing catalytic performance,setting the stage for the advancement of superior catalysts.展开更多
Biomass-derived hard carbons,usually prepared by pyrolysis,are widely considered the most promising anode materials for sodium-ion bat-teries(SIBs)due to their high capacity,low poten-tial,sustainability,cost-effectiv...Biomass-derived hard carbons,usually prepared by pyrolysis,are widely considered the most promising anode materials for sodium-ion bat-teries(SIBs)due to their high capacity,low poten-tial,sustainability,cost-effectiveness,and environ-mental friendliness.The pyrolysis method affects the microstructure of the material,and ultimately its so-dium storage performance.Our previous work has shown that pyrolysis in a sealed graphite vessel im-proved the sodium storage performance of the car-bon,however the changes in its microstructure and the way this influences the sodium storage are still unclear.A series of hard carbon materials derived from corncobs(CCG-T,where T is the pyrolysis temperature)were pyrolyzed in a sealed graphite vessel at different temperatures.As the pyrolysis temperature increased from 1000 to 1400℃ small carbon domains gradually transformed into long and curved domains.At the same time,a greater number of large open pores with uniform apertures,as well as more closed pores,were formed.With the further increase of pyrolysis temperature to 1600℃,the long and curved domains became longer and straighter,and some closed pores gradually became open.CCG-1400,with abundant closed pores,had a superior SIB performance,with an initial reversible ca-pacity of 320.73 mAh g^(-1) at a current density of 30 mA g^(-1),an initial Coulomb efficiency(ICE)of 84.34%,and a capacity re-tention of 96.70%after 100 cycles.This study provides a method for the precise regulation of the microcrystalline and pore structures of hard carbon materials.展开更多
In response to the limitations of conventional chemical synthesis methods for the structural modulation of nanomaterials,an innovative high magnetic field-assisted wet chemical synthesis method was proposed to prepare...In response to the limitations of conventional chemical synthesis methods for the structural modulation of nanomaterials,an innovative high magnetic field-assisted wet chemical synthesis method was proposed to prepare NiFe_(2)O_(4)/Fe_(2)O_(3) heterostructures.It is found that the high-energy physical field could induce a more homogeneous morphology of NiFe_(2)O_(4)/Fe_(2)O_(3),accompanied by phase transformation from Fe_(2)O_(3) to NiFe_(2)O_(4).As a result,the optimized structure obtained under the magnetic field endows NiFe_(2)O_(4)/Fe_(2)O_(3) with enhanced performance for the lithium-ion battery anode,as evidenced by an increase of 16%(1200 mA·h/g)in discharge capacity and 24% in ultra-stable cycling performance(capacity retention of 97.1%).These results highlight the feasibility of high magnetic fields in modulating material structure and enhancing lithium storage performance.展开更多
Sodium-ion batteries(SIBs)have attracted significant attentions as promising alternatives to lithium-ion batteries for large-scale energy storage applications.Here carbon materials are considered as the most competiti...Sodium-ion batteries(SIBs)have attracted significant attentions as promising alternatives to lithium-ion batteries for large-scale energy storage applications.Here carbon materials are considered as the most competitive anodes for SIBs based on their low-cost,abundant availability and excellent structural stability.Pitch,with high carbon content and low cost,is an ideal raw precursor to prepare carbon materials for large-scale applications.Nevertheless,the microstructures of pitch-based carbon are highly ordered with smaller interlayer distances,which are unfavorable for Na ion storage.Many efforts have been made to improve the sodium storage performance of pitch-based carbon materials.This review summarizes the recent progress about the application of pitch-based carbons for SIBs anodes in the context of carbon’s morphology and structure regulation strategies,including morphology adjustment,heteroatoms doping,fabricating heterostructures,and the increase of the degree of disorder.Besides,the advantages,present challenges,and possible solutions to current issues in pitch-based carbon anode are discussed,with the highlight of future research directions.This review will provide a deep insight into the development of low-cost and high-performance pitch-based carbon anode for SIBs.展开更多
The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity...The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.展开更多
Nanoporous metals have received significant attention as a new class of structural and functional materials.However,the macroscopic brittle fracture under the tensile test is an impediment to their practical applicati...Nanoporous metals have received significant attention as a new class of structural and functional materials.However,the macroscopic brittle fracture under the tensile test is an impediment to their practical applications.Thus,it is of central importance to develop nanoporous materials with low cost and high tensile ductility.Herein,a nanoporous Cu film supported on a pure Cu substrate(NPC@Cu)was fabricated by utilizing a liquid Ga assisted alloying-dealloying strategy,and the thickness of NPC film can be precisely regulated by changing the mass loading of liquid Ga.In-situ X-ray diffraction was performed to further explore the alloying/dealloying mechanisms.The NPC@Cu films show good tensile mechanical properties with a minimum elongation of 13.5%,which can be attributed to the good interface bonding and certain modulus matching between the nanoporous Cu layer and the Cu substrate.Our findings demonstrate that the design of film-substrate structure provides a feasible strategy for enhancing the mechanical properties of nanoporous metals.展开更多
Layered materials with two-dimensional ion diffusion channels and fast kinetics are attractive as cathode materials for secondary batteries.However,one main challenge in potassium-ion batteries is the large ion size o...Layered materials with two-dimensional ion diffusion channels and fast kinetics are attractive as cathode materials for secondary batteries.However,one main challenge in potassium-ion batteries is the large ion size of K^(+),along with the strong K^(+)-K^(+)electrostatic repulsion.This strong interaction results in initial K deficiency,greater voltage slope,and lower specific capacity between set voltage ranges for layered transition metal oxides.In this review,a comprehensive review of the latest advancements in layered cathode materials for potassium-ion batteries is presented.Except for layered transition metal oxides,some polyanionic compounds,chalcogenides,and organic materials with the layered structure are introduced separately.Furthermore,summary and personal perspectives on future optimization and structural design of layered cathode materials are constructively discussed.We strongly appeal to the further exploration of layered polyanionic compounds and have demonstrated a series of novel layered structures including layered K_(3)V_(2)(PO_(4))_(3).展开更多
Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites...Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.展开更多
The development of low-cost, efficient, and high atomic economy electrocatalysts for hydrogen evolution reaction(HER) in the entire p H range for sustainable hydrogen production is of great importance but still challe...The development of low-cost, efficient, and high atomic economy electrocatalysts for hydrogen evolution reaction(HER) in the entire p H range for sustainable hydrogen production is of great importance but still challenging. Herein, we synthesize a highly dispersed N-doped carbon frames(NCFs) anchored with Co single atoms(SAs) and Co nanoparticles(NPs) catalyst by a doping-adsorption-pyrolysis strategy for electrocatalytic hydrogen evolution. The Co SAs-Co NPs/NCFs catalyst exhibits an excellent HER activity with small overpotential, low Tafel slope, high turnover frequency as well as remarkable stability. It also exhibits a superior HER performance in the entire p H range. Combining with experimental and theoretical calculation, we find that Co SAs with Co-N_(3) coordination structure and Co NPs have a strong interaction for promoting synergistic HER electrocatalytic process. The H_(2)O molecule is easily activated and dissociated on Co NPs, while the generated H^(*) is easily adsorbed on Co SAs for HER, which makes the Co SAs-Co NPs/NCFs catalyst exhibit more suitable H adsorption strength and more conducive to the activation and dissociation of H_(2)O molecules. This work not only proposes a novel idea for constructing coupling catalyst with atomic-level precision, but also provides strong reference for the development of high-efficiency HER electrocatalysts for practical application.展开更多
文摘By virtue of a 3∶1 complementary coordination strategy,a chiral heteroleptic metal-organic cage that con-tains divergent functional units,Pd‑R(Zn),was precisely constructed via self-assembly of monodentate variational Zn-salen ligands RZn and NADH(reduced nicotinamide adenine dinucleotide)mimic modified tridentate ligands with square-planar Pd ions.UV-Vis and luminescence spectra experiments reveal that different anions could selec-tively interact with different sites of Zn-salen modified metal-organic cages to achieve the structural regulation of cage compound,by using the differentiated host-vip electrostatic interactions of counter ions with metal-organic hosts.Compared to other anions,the presence of chloride ions caused the most significant fluorescence emission enhancement of Pd‑R(Zn),meanwhile,the UV-Vis absorption band attributed to the salen aromatic backbone showed an absorption decrease,and the metal-to-ligand induced peak displayed a blue shift effect.Circular dichro-ism and ^(1)H NMR spectra further demonstrate that the introduction of chloride anions is beneficial to keeping a more rigid scaffold.
基金supported by the National Research Foundation(NRF)grants(2022R1A4A1032832 and 2019R1A6A1A10073079)funded by the Korean government(MSIT)
文摘Aqueous zinc-ion batteries(ZIBs)have shown great potential in the fields of wearable devices,consumer electronics,and electric vehicles due to their high level of safety,low cost,and multiple electron transfer.The layered cathode materials of ZIBs hold a stable structure during charge and discharge reactions owing to the ultrafast and straightforward(de)intercalation-type storage mechanism of Zn^(2+)ions in their tunable interlayer spacing and their abilities to accommodate other vip ions or molecules.Nevertheless,the challenges of inadequate energy density,dissolution of active materials,uncontrollable byproducts,increased internal pressure,and a large de-solvation penalty have been deemed an obstacle to the development of ZIBs.In this review,recent strategies on the structure regulation of layered materials for aqueous zinc-ion energy storage devices are systematically summarized.Finally,critical science challenges and future outlooks are proposed to guide and promote the development of advanced cathode materials for ZIBs.
基金supported by the National Natural Science Foundation of China(Grant No.22108306)the Taishan Scholars Program of Shandong Province(Grant No.tsqn201909065)the Shandong Provincial Natural Science Foundation(Grant Nos.ZR2021YQ15,ZR2020QB174)。
文摘The development and utilization of renewable clean energy can effectively solve the two major problems of energy and environment. As an efficient power generation device that converts hydrogen energy into electric energy, fuel cell has attracted more and more attention. For fuel cells, the oxygen reduction reaction(ORR) at the cathode is the core reaction, and the design and development of high-performance ORR catalysts remain quite challenging. Since the microenvironment of the active center of single atom catalysts(SACs) has an important influence on its catalytic performance, it has been a research focus to improve the ORR activity and stability of electrocatalysts by adjusting the structure of the active center through reasonable structural regulation methods. In this review, we reviewed the preparation and structure–activity relationship of SACs for ORR. Then, the structural precision regulation methods for improving the activity and stability of ORR electrocatalysts are discussed. And the advanced in-situ characterization techniques for revealing the changes of active sites in the electrocatalytic ORR process are summarized. Finally, the challenges and future design directions of SACs for ORR are discussed. This work will provide important reference value for the design and synthesis of SACs with high activity and stability for ORR.
文摘Benefiting from the ultrahigh specific surface areas,highly accessible surface atoms,and highly tunable microscopic structures,the two-dimensional metallenes as nanocatalysts have displayed promising performance for various electrocatalytic reactions.Herein,we reviewed recent advances on metallenes in structural regulations including defect,phase,strain,interface,doping,and alloying engineering strategies and their applications in energy electrocatalytic reactions involving oxygen reduction reaction,carbon dioxide reduction reaction,hydrogen evolution reaction,and small molecules oxidation reaction.Finally,we proposed the future challenges and directions in this emerging area.
文摘Based on the overall consideration of individual behaviors of Ricardian and non-Ricardian households, this paper develops a New Keynesian dynamic stochastic general equilibrium(DSGE) model to form a relatively systematic research framework for analyzing the economic effects of structural fiscal instruments. Our study findsthat great differences exist in the macroeconomic effects of different fiscal instruments, suggesting that the government should prudently select these fiscal instruments in fiscal macro-control. The simulating results of fiscal shocks show that the effect of tax cut is superior to the effect of increased spending. In the context of slowing economic growth and less potent stimulation policy, the government should transform its previous regulatory approach of fiscal policy and shift from hefty spending stimulus policy to structural tax cuts. This paper believes that China should step up the implementation of public-private partnership, increase its spending on social security, healthcare, pension and public services and facilitate the transition toward a service-based government; and that tax policy should focus on structural tax cuts on consumption to promote the transition of demand structure toward consumption-driven.
基金supported by Hunan Provincial Key Laboratory of Micro&Nano Materials Interface Science,China,the National Natural Science Foundation of China(Nos.21773311,21972169)the Hunan Provincial Science and Technology Plan Project,China(No.2019TP1001)the Open Sharing Fund for the Large-scale Instruments and Equipments of Central South University,China.
文摘To address the ever-increasing CO_(2)concentration problem in the atmospheric air arisen by massive consumption of fossil fuels,electrocatalytic technologies that reduce CO_(2)to generate high value-added products have been gaining increasing interest.Cu-based CO_(2)reduction catalysts have attracted widespread attention owing to their capability of generating C1 and C_(2+)products.However,Cu-based catalysts are highly challenged by their low product selectivity.Recently,Cu-based bimetallic catalysts have been found the unique catalytical activity and selectivity in CO_(2)reduction reactions(CO_(2)RR).The incorporation of other metals can change the electronic circumstance of Cu-based catalysts,promoting the adsorption ability of the intermediate products and consequently leading to high selectivity.In this minireview,we intend to summarize recent advances of Cu-based bimetallic catalysts in producing C1 and C_(2+)products,involving designing heterostructure,alloy,defects and surface modification engineering.We pay special attention to the regulation of electronic structure of the composite catalysts,as well as insights into the relationship between electronic property and catalytical performance for Cu-based bimetallic catalysts.
基金supported by the National Natural Science Foundation of China(No.2012BAD20B04)
文摘The title compound 1-（3-amino-[1,2,4]triazol-1-yl）-3,3-dimethyl-butan-2-one（3） was synthesized by Hofmann-alkylation reaction of 1-chloro-3,3-dimethyl-butan-2-one（1） and ~1H-[1,2,4]triazol-3-ylamine（2） with equal amount of K_2CO_3 as acid acceptor. The structure of compound 3 was characterized by ~1H NMR, 13 C NMR, HRMS and single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P21/n with a = 5.7227（8）, b = 27.924（4）, c = 6.2282（7） ？, β = 101.892（11）°, V = 973.9（2） ？~3, Z = 4, T = 180.00（10） K, μ（MoKα） = 0.087 mm^（-1）, Dc = 1.243 g/cm^3, 3832 reflections measured（3.648≤θ≤26.022°）, 1916 unique reflections（Rint = 0.0359, Rsigma = 0.0572） used in all calculations. The final R = 0.0557（I 〉 2σ（I）） and w R = 0.1276（all data）. Bioassay showed that 3 displayed excellent activity as plant growth regulator with inducing lateral root formation and enhancing primary root elongation at 0.27 mmol/L（50 ppm） in soybeen（He Feng-50）. Good water solubility was found with 50 mg in 1 m L of water. Therefore, application of 3 in agriculture is more environmentally friendly due to cosolvent-free condition, and results in improved abiotic-stress tolerance by affecting the root growth. And furthermore, it can be used as a precursor to investigate the function of regulating plant root growth.
基金supported by the National Natural Science Foundation of China(grant no.22171157).
文摘Atomically dispersed catalysts(ADCs)have been diffusely researched for the development of advanced catalytic processes owing to their welldefined structure,high atomic utilization,and outstanding activity.Precisely decoding the intrinsic structures and coordination microenvironments of ADCs still confronts significant challenges.Overcoming these challenges is important for profound understanding of the structure-activity relationships and directing the future design of ADCs.Herein,this minireview summarizes recent progress and advanced characterization techniques for the engineering of ADCs,including single-atom catalysts,dualatom catalysts,and atomic cluster catalysts with regard to precise synthesis,structural regulation,and the structure-performance relationship.The catalytic merits and regulation strategies of recent breakthroughs in energy conversion,enzyme mimicry,and organic synthesis are thoroughly discussed to disclose the catalytic mechanism-guided ADCs design.Finally,a comprehensive summary of the future challenges and potential prospects is presented to stimulate more design and application possibilities for ADCs.We believe that this comprehensive minireview will open up novel pathways for the widespread utilization of ADCs in diverse catalytic processes.
基金financially supported by the National Natural Science Foundation of China(Nos.22168040 and 22162025)the Project of Science&Technology Office of Shannxi Province(No.2022JM-062)。
文摘At present,industrial synthetic ammonia was still obtained through the Hubble-Bosch process,with large energy consumption.It is a research hotspot to realize green synthetic ammonia by using solar energy.The difficulty of photocatalytic ammonia synthesis was that the photo-excited electrons have not enough energy to active N≡N.In this study,Ti was doped into BiOBr by one-step hydrothermal method,which was oxidized into TiO_(2)when the doping amount reaches the maximum,in situ forming Ti_(0.31)B_(0.69)OB/TiO_(2)composites.Benefiting from the synergistic effect of Ti doping and S-scheme heterojunction,the synthetic ammonia efficiency of Ti_(0.31)B_(0.69)OB/TiO_(2)-11.96 reached 1.643 mmol·g_(cat)^(-1)at mild conditions and without hole scavenger for up to 7 h,the efficiency of synthetic ammonia is 115 times,10.5 times and 3.3 times of that of BiOBr,Ti_(0.31)B_(0.69)OB and TiO_(2),respectively.Specifically,DFT calculation confirms that Ti doping accurately refine the electronic structure of BiOBr,facilitate nitrogen adsorption activation and reduce hydrogenation reaction energy barrier,thus accelerating the reaction kinetics of photocatalytic nitrogen reduction(NRR),Meanwhile,constructing S-scheme heterojunction boosts the separation and transfer of photogenerated electron-hole pairs,improving the reduction ability of electrons in the conduction band of TiO_(2)and the oxidation ability of holes in the valence band of Ti_(0.31)B_(0.69)OB.
基金This work was financially supported by the National Natural Science Foundation of China(NSFC)(No.22308336)the City University of Hong Kong start-up fund.
文摘Sunlight-driven photocatalysis,which can produce clean fuels and mitigate environmental pollution,has received extensive research attention due to its potential for addressing both energy shortages and environmental crises.Bismuth(Bi)-based photocatalysts with broad spectrum solar-light absorption and tunable structures,exhibit promising applications in solar-driven photocatalysis.Oxygen vacancy(OV)engineering is a widely recognized strategy that shows great potential for accelerating charge separation and small molecule activation.Based on OV engineering,this review focuses on Bi-based photocatalysts and provides a comprehensive overview including synthetic methods,regulation strategies,and applications in photocatalytic field.The synthetic methods of Bibased photocatalysts with OVs(BPOVs)are classified into hydrothermal,solvothermal,ultraviolet light reduction,calcination,chemical etching,and mechanical methods based on different reaction types,which provide the possibility for the structural regulation of BPOVs,including dimensional regulation,vacancy creation,elemental doping,and heterojunction fabrication.Furthermore,this review also highlights the photocatalytic applications of BPOVs,including CO_(2)reduction,N2 fixation,H2 generation,O_(2)evolution,pollutant degradation,cancer therapy,and bacteria inactivation.Finally,the conclusion and prospects toward the future development of BPOVs photocatalysts are presented.
基金financially supported by Shenzhen Bureau of Science,Technology and Innovation Commission(No.JSGG20200914113601003)the National Natural Science Foundation of China(No.51971080)。
文摘The inherent electrocatalytic potential of transition metal phosphides(TMPs)for oxygen evolution is influenced by the reduced efficiency of electron transfer resulting from the interaction between electronegative phosphorus atoms and transition metals.Here,we introduce Fe into Ni_(2)P nanocrystals by thermal injection synthesis method,and anchor them on nickel foam(NF)by facile spraying to prepare self-supporting oxygen evolution reaction(OER)electrocatalyst.Promisingly,the optimized electrode of Ni_(2)P-Fe-2/NF demonstrates low overpotentials of 212 mV with 10 mA·cm^(-2)and a 0.9%decay within300 h test of 50 mA·cm^(-2).Notably,when electrode size was expanded to 600 cm^(2)and applied to a larger electrolyzer,its 9 h decay rate at 6 A current was only 1.69%.Characterization results show that Fe doped NiOOH is generated during OER reaction as actual catalyst,Results from density functional theory(DFT)computations suggest that Fe doping shifts NiOOH d-band center to Fermi level,lowering critical *OOH intermediates formation energy barrier during the OER reaction.These findings inform the large-scale industrial application of TMPs as robust electrocatalysts.
基金supported by the National Key R&D Program of China(2021YFA0716302,2018YFA0703603)the Guangdong Basic and Applied Basic Research Foundation(2023A1515110145)+3 种基金the National Natural Science Foundation of China(52192602,52130108,62488201,52171149)the China Postdoctoral Science Foundation(2024M762276)the Fundamental Research Funds for the Central Universities(30919011404)the support by the Qing Lan project and the specially-appointed professor project of Jiangsu province.
文摘The pursuit of highly efficient catalysts for the urea oxidation reaction(UOR)represents a pivotal and sustainable approach to the generation of renewable energy.Structural regulation has emerged as a particularly effective approach to achieving superior catalytic performance.However,in the realm of amorphous catalysts with disordered structure and remarkable catalytic potential,identifying effective regulation strategies to enhance the UOR performance remains a formidable yet critical challenge.In this study,we present a coupling modulation strategy based on the growth mode and pulse current,utilizing pulse electrodeposition(PED)to achieve amorphous Ni-P catalysts with high-efficiency UOR performance.Amorphous Ni/Ni-P catalyst engineered by Stranski-Krastanov(SK)growth mode along with low pulse current exhibits unprecedented catalytic activity for UOR,as evidenced by its overpotential of 1.35 V at 10 mA/cm^(2) and 1.37 V@100 mA/cm^(2).We reveal the regulation-relationship among the growth modes,catalyst structure and UOR performance by PED.We also show that low-pulse current can efficiently enhance UOR performance by elevating energy states in amorphous Ni-P,and further demonstrate the broad applicability across diverse growth modes.Therefore,by integrating film growth modes with a pulse current,we have established a novel method for significantly enhancing catalytic performance,setting the stage for the advancement of superior catalysts.
文摘Biomass-derived hard carbons,usually prepared by pyrolysis,are widely considered the most promising anode materials for sodium-ion bat-teries(SIBs)due to their high capacity,low poten-tial,sustainability,cost-effectiveness,and environ-mental friendliness.The pyrolysis method affects the microstructure of the material,and ultimately its so-dium storage performance.Our previous work has shown that pyrolysis in a sealed graphite vessel im-proved the sodium storage performance of the car-bon,however the changes in its microstructure and the way this influences the sodium storage are still unclear.A series of hard carbon materials derived from corncobs(CCG-T,where T is the pyrolysis temperature)were pyrolyzed in a sealed graphite vessel at different temperatures.As the pyrolysis temperature increased from 1000 to 1400℃ small carbon domains gradually transformed into long and curved domains.At the same time,a greater number of large open pores with uniform apertures,as well as more closed pores,were formed.With the further increase of pyrolysis temperature to 1600℃,the long and curved domains became longer and straighter,and some closed pores gradually became open.CCG-1400,with abundant closed pores,had a superior SIB performance,with an initial reversible ca-pacity of 320.73 mAh g^(-1) at a current density of 30 mA g^(-1),an initial Coulomb efficiency(ICE)of 84.34%,and a capacity re-tention of 96.70%after 100 cycles.This study provides a method for the precise regulation of the microcrystalline and pore structures of hard carbon materials.
基金supported by the National Natural Science Foundation of China(No.52274294)the Fundamental Research Funds for the Central Universities,China(No.N2124007-1)the Fund of the State Key Laboratory of Solidification Processing in Northwestern Polytechnical University,China(No.SKLSP202101)。
文摘In response to the limitations of conventional chemical synthesis methods for the structural modulation of nanomaterials,an innovative high magnetic field-assisted wet chemical synthesis method was proposed to prepare NiFe_(2)O_(4)/Fe_(2)O_(3) heterostructures.It is found that the high-energy physical field could induce a more homogeneous morphology of NiFe_(2)O_(4)/Fe_(2)O_(3),accompanied by phase transformation from Fe_(2)O_(3) to NiFe_(2)O_(4).As a result,the optimized structure obtained under the magnetic field endows NiFe_(2)O_(4)/Fe_(2)O_(3) with enhanced performance for the lithium-ion battery anode,as evidenced by an increase of 16%(1200 mA·h/g)in discharge capacity and 24% in ultra-stable cycling performance(capacity retention of 97.1%).These results highlight the feasibility of high magnetic fields in modulating material structure and enhancing lithium storage performance.
基金financially supported by the Beijing Municipal Science and Technology Commission(Grant No.Z181100004718007)the National Key R&D Program of China(Grant No.2017YFB0102204)。
文摘Sodium-ion batteries(SIBs)have attracted significant attentions as promising alternatives to lithium-ion batteries for large-scale energy storage applications.Here carbon materials are considered as the most competitive anodes for SIBs based on their low-cost,abundant availability and excellent structural stability.Pitch,with high carbon content and low cost,is an ideal raw precursor to prepare carbon materials for large-scale applications.Nevertheless,the microstructures of pitch-based carbon are highly ordered with smaller interlayer distances,which are unfavorable for Na ion storage.Many efforts have been made to improve the sodium storage performance of pitch-based carbon materials.This review summarizes the recent progress about the application of pitch-based carbons for SIBs anodes in the context of carbon’s morphology and structure regulation strategies,including morphology adjustment,heteroatoms doping,fabricating heterostructures,and the increase of the degree of disorder.Besides,the advantages,present challenges,and possible solutions to current issues in pitch-based carbon anode are discussed,with the highlight of future research directions.This review will provide a deep insight into the development of low-cost and high-performance pitch-based carbon anode for SIBs.
基金Changjiang Scholars Program of the Ministry of Education,Grant/Award Number:Q2018270Outstanding Youth Funding of Anhui Province,Grant/Award Number:OUFAH 1908085J10+2 种基金Jiangsu Students'Innovation and Entrepreneurship Training Program,Grant/Award Number:202111117079YNatural Science Foundation of Jiangsu Province,Grant/Award Number:BK20200044National Natural Science Foundation of China,Grant/Award Numbers:NSFC 21671004,NSFC 21975001,NSFC U1904215。
文摘The ferrocene(Fc)-based metal-organic frameworks(MOFs)are regarded as compelling platforms for the construction of efficient and robust oxygen evolution reaction(OER)electrocatalysts due to their superior conductivity and flexible electronic structure.Herein,density functional theory simulations were addressed to predict the electronic structure regulations of CoFc-MOF by nickel doping,which demonstrated that the well-proposed CoNiFc-MOFs delivered a small energy barrier,promoted conductivity,and well-regulated d-band center.Inspired by these,a series of sea-urchin-like CoNiFc-MOFs were successfully synthesized via a facile solvothermal method.Moreover,the synchrotron X-ray and X-ray photoelectron spectroscopy measurements manifested that the introduction of nickel could tailor the electronic structure of the catalyst and induce the directional transfer of electrons,thus optimizing the rate-determining step of^(*)O→^(*)OOH during the OER process and yielding decent overpotentials of 209 and 252 mV at 10 and 200 mA cm^(−2),respectively,with a small Tafel slope of 39 mV dec^(−1).This work presents a new paradigm for developing highly efficient and durable MOF-based electrocatalysts for OER.
基金supported by the National Natural Science Foundation of China(Grant No.51871133)the Taishan Scholar Foundation of Shandong Province,the Program of Jinan Science and Technology Bureau(Grant No.2019GXRC001)the Major Projects of Guangdong Education Department for Foundation Research and Applied Research,China(Grant No.2019KZDXM065).
文摘Nanoporous metals have received significant attention as a new class of structural and functional materials.However,the macroscopic brittle fracture under the tensile test is an impediment to their practical applications.Thus,it is of central importance to develop nanoporous materials with low cost and high tensile ductility.Herein,a nanoporous Cu film supported on a pure Cu substrate(NPC@Cu)was fabricated by utilizing a liquid Ga assisted alloying-dealloying strategy,and the thickness of NPC film can be precisely regulated by changing the mass loading of liquid Ga.In-situ X-ray diffraction was performed to further explore the alloying/dealloying mechanisms.The NPC@Cu films show good tensile mechanical properties with a minimum elongation of 13.5%,which can be attributed to the good interface bonding and certain modulus matching between the nanoporous Cu layer and the Cu substrate.Our findings demonstrate that the design of film-substrate structure provides a feasible strategy for enhancing the mechanical properties of nanoporous metals.
基金supported by the Natural Science Foundation of Jiangsu Province of China(BK20180086)
文摘Layered materials with two-dimensional ion diffusion channels and fast kinetics are attractive as cathode materials for secondary batteries.However,one main challenge in potassium-ion batteries is the large ion size of K^(+),along with the strong K^(+)-K^(+)electrostatic repulsion.This strong interaction results in initial K deficiency,greater voltage slope,and lower specific capacity between set voltage ranges for layered transition metal oxides.In this review,a comprehensive review of the latest advancements in layered cathode materials for potassium-ion batteries is presented.Except for layered transition metal oxides,some polyanionic compounds,chalcogenides,and organic materials with the layered structure are introduced separately.Furthermore,summary and personal perspectives on future optimization and structural design of layered cathode materials are constructively discussed.We strongly appeal to the further exploration of layered polyanionic compounds and have demonstrated a series of novel layered structures including layered K_(3)V_(2)(PO_(4))_(3).
文摘Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.
基金supported by the Taishan Scholars Program of Shandong Province(tsqn201909065)the Shandong Provincial Natural Science Foundation(ZR2020QB174)+3 种基金the Petro China Innovation Foundation(2019D-5007-0401)the National Natural Science Foundation of China(21776315,22108306)the Fundamental Research Funds for the Central Universities(19CX02008A,19CX05001A)the Postgraduate Innovation Fund of China University of Petroleum(East China)(YCX2020037)。
文摘The development of low-cost, efficient, and high atomic economy electrocatalysts for hydrogen evolution reaction(HER) in the entire p H range for sustainable hydrogen production is of great importance but still challenging. Herein, we synthesize a highly dispersed N-doped carbon frames(NCFs) anchored with Co single atoms(SAs) and Co nanoparticles(NPs) catalyst by a doping-adsorption-pyrolysis strategy for electrocatalytic hydrogen evolution. The Co SAs-Co NPs/NCFs catalyst exhibits an excellent HER activity with small overpotential, low Tafel slope, high turnover frequency as well as remarkable stability. It also exhibits a superior HER performance in the entire p H range. Combining with experimental and theoretical calculation, we find that Co SAs with Co-N_(3) coordination structure and Co NPs have a strong interaction for promoting synergistic HER electrocatalytic process. The H_(2)O molecule is easily activated and dissociated on Co NPs, while the generated H^(*) is easily adsorbed on Co SAs for HER, which makes the Co SAs-Co NPs/NCFs catalyst exhibit more suitable H adsorption strength and more conducive to the activation and dissociation of H_(2)O molecules. This work not only proposes a novel idea for constructing coupling catalyst with atomic-level precision, but also provides strong reference for the development of high-efficiency HER electrocatalysts for practical application.
