The development of clean and sustainable energy sources has received widespread interest in the past few decades due to the rolling energy demands while extenuating the rising tiers of greenhouse gases and environment...The development of clean and sustainable energy sources has received widespread interest in the past few decades due to the rolling energy demands while extenuating the rising tiers of greenhouse gases and environmental pollution.Due to their intermittent nature,these green and sustainable sources require appropriate energy storage systems.Amongst different energy storage technologies,electrochemical energy storage devices,particularly supercapacitors(SCs),have fascinated global attention for their utilization in electric vehicles,power supports,portable electronics,and many others application requiring electric energy devices for their operation.Thus,the growth of SCs in the commercial market has squeezed requirements,and further developments are obligatory for their effective industrialization.In the meantime,SCs also face technical complications and contests for their introduction in industrial settings because of their low energy density and high Levelized cost.The present study combines core strengths,weaknesses,opportunities,and threats(SWOT)analysis of SCs with new perspectives and recent ideas.The challenges and the future progressive prospects of SCs are also presented in detail.This review will afford consistent direction and new superhighways for the further development of SCs as standalone and complementary energy storage systems.展开更多
Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorga...Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.展开更多
Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been ...Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.展开更多
Boron nitride(BN) nanostructures with complementary functions to their carbon counterparts are one of the most intriguing nanomaterials.Here we devote a compact review on the syntheses of BN nanomaterials:typical zero...Boron nitride(BN) nanostructures with complementary functions to their carbon counterparts are one of the most intriguing nanomaterials.Here we devote a compact review on the syntheses of BN nanomaterials:typical zero-dimensional(OD) fullerenes and nanoparticles,one-dimensional(1D) nanotubes and nanoribbons,two-dimensional(2D) nanosheets as well as three-dimensional(3D) nanoporous BN.Combining low-dimensional quantum confinement and surface effects with unique physical and chemical properties of BN,e.g.excellent electric insulation,wide band gap,and high chemical and thermal stability,BN nanomaterials have drawn particular attention in a variety of potential applications,e.g.luminescence,functional composites,hydrogen accumulators,and advanced insulators,which are also reviewed.展开更多
Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen...Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.展开更多
Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many are...Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.展开更多
The lattice-oxygen-mediated mechanism is considered as a reasonable mechanism for the electrochemical catalytic oxygen evolution reaction(OER)of NiFe layered double hydroxides(LDHs).A NiFe LDH with distinct lattice co...The lattice-oxygen-mediated mechanism is considered as a reasonable mechanism for the electrochemical catalytic oxygen evolution reaction(OER)of NiFe layered double hydroxides(LDHs).A NiFe LDH with distinct lattice contraction and microcrystallization was synthesized via a simple one-step method using sodium gluconate.The lattice contraction is attributed to the interaction of carbon in sodium gluconate and iron in NiFe LDH.The NiFe LDH with optimized microcrystallization and lattice contraction shows a low overpotential of 217 mV at a current density of 10 mA cm^(−2) and excellent durability of 20 h at a high current density of 100 mA cm^(−2).The results revealed that a contractive metal–oxygen bond could boost the intrinsic activity of active sites and the microcrystallization promotes an increase in the number of active sites in terms of unit area.The chemical environment of oxygen elemental characterization and resistance at different chronopotentiometry times confirm that the lattice oxygen element is indeed involved in the process of OER,supporting the lattice-oxygen-mediated mechanism of NiFe LDH.Density functional theory calculations reveal that contractive metal–oxygen bonds induced a reduction of the adsorption energy barrier of intermediate products,thus improving the intrinsic catalytic activity.The special characteristics of microcrystallization and lattice contraction of NiFe LDH provide a strategy to improve both the number and the intrinsic activity of active sites in a versatile manner.展开更多
√√The electronic structures of monolayer silicenes(4 × 4 and■ ×■R13.9o) grown on Ag(111) surface are studied by scanning tunneling spectroscopy(STS) and density functional theory(DFT) calculations. While...√√The electronic structures of monolayer silicenes(4 × 4 and■ ×■R13.9o) grown on Ag(111) surface are studied by scanning tunneling spectroscopy(STS) and density functional theory(DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states.The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations.展开更多
Photocatalytic conversion of CO_(2)into solar fuels provides a bright route for the green and sustainable development of human society.However,the realization of efficient photocatalytic CO_(2)reduction reaction(CO_(2...Photocatalytic conversion of CO_(2)into solar fuels provides a bright route for the green and sustainable development of human society.However,the realization of efficient photocatalytic CO_(2)reduction reaction(CO_(2)RR)is still challenging owing to the sluggish kinetics or unfavorable thermodynamics for basic chemical processes of CO_(2)RR,such as adsorption,activation,conversion and product desorption.To overcome these shortcomings,recent works have demonstrated that surface engineering of semiconductors,such as introducing surface vacancy,surface doping,and cocatalyst loading,serves as effective or promising strategies for improved photocatalytic CO_(2)RR with high activity and selectivity.The essential reason lies in the activation and reaction pathways can be optimized and regulated through the reconstruction of surface atomic and electronic structures.Herein,in this review,we focus on recent research advances about rational design of semiconductor surface for photocatalytic CO_(2)RR.The surface engineering strategies for improved CO_(2)adsorption,activation,and product selectivity will be reviewed.In addition,theoretical calculations along with in situ characterization techniques will be in the spotlight to clarify the kinetics and thermodynamics of the reaction process.The aim of this review is to provide deep understanding and rational guidance on the design of semiconductors for photocatalytic CO_(2)RR.展开更多
Aprotic lithium–oxygen batteries(LOBs)have been recognized as novel energy storage devices for their outstanding specific energy density,while the large discharge/charge overpotential is a tough barrier to be overcom...Aprotic lithium–oxygen batteries(LOBs)have been recognized as novel energy storage devices for their outstanding specific energy density,while the large discharge/charge overpotential is a tough barrier to be overcome.Here,hetero-structured MoS_(2)/ZnIn_(2)S_(4) nanosheets have been prepared to capture visible light and the generated charge carriers are utilized for promoting both the oxygen reduction reaction and the oxygen evolution reaction.With the light illumination in the discharge process,the abundant photo-inspired electrons serve as the reaction sites to promote the reduction of O_(2) into LiO_(2) which is finally deposited as Li_(2)O_(2).On the contrary,the generated holes in the valence band can contribute to the low oxidization potential of Li_(2)O_(2) during the charge process.It delivers a low charge potential of 3.29 V,with an excellent resulting energy efficiency of 96.7%,much superior to that of 69.2%in the dark condition.It is noted that the involvement of photoelectrons has influenced the growth of Li_(2)O_(2) films on the MoS_(2)/ZnIn_(2)S_(4) nanosheets through the surface-adsorption pathway.The insights from the theoretical calculation confirm that the photoelectrons favor the absorption of LiO_(2) and the formation of the Li_(2)O_(2) film through the surface route.Therefore,this paper provides a deeper understanding of the mechanism of photoinspired charge carriers in LOBs and will enable further exploration of photo-involved energy storage systems.展开更多
Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step ...Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.展开更多
Low activation isotopic boron(11B)based magnesium diboride(Mg^(11)B_(2))superconductors doped with biomass-derived activated carbon were synthesized using11B and magnesium powder via solid-state reaction.The effect of...Low activation isotopic boron(11B)based magnesium diboride(Mg^(11)B_(2))superconductors doped with biomass-derived activated carbon were synthesized using11B and magnesium powder via solid-state reaction.The effect of carbon doping on the lattice structure and superconducting properties of Mg^(11)B_(2)bulks were evaluated using X-ray powder diffraction,high resolution transmission electron microscopy,scanning electron microscopy and magnetization measurements.Precise refinement of structural parameters indicates successful substitution of carbon in Mg^(11)B_(2)bulks.The critical current density(Jc)of carbon doped Mg^(11)B_(2)synthesized at 650℃was enhanced more than two times compared with the pure Mg^(11)B_(2)bulk.Similar improvement was observed for the Mg^(11)B_(2)bulks heat-treated at 800℃.This enhancement is due to successful substitution of biomass-derived carbon with high surface area into Mg^(11)B_(2)lattice.The flux pinning mechanism of pure and doped Mg^(11)B_(2)bulks were investigated using the Dew-Hughes model.This study provides information regarding enhancement of the Jc of low activation Mg^(11)B_(2)superconductors suitable for next-generation fusion magnets.展开更多
To effectively alleviate the ever-increasing energy crisis and environmental issues,clean and sustainable energy-related materials as well as the corresponding storage/conversion devices are in urgent demand.Silicon(S...To effectively alleviate the ever-increasing energy crisis and environmental issues,clean and sustainable energy-related materials as well as the corresponding storage/conversion devices are in urgent demand.Silicon(Si) with the second most elemental abundance on the crust in the form of silicate or silica(SiO_(2)) minerals,is an advanced emerging material showing high performance in energy-related fields(e.g.batteries,photocatalytic hydrogen evolution).For the improved performance in industry-scale applications,Si materials with delicate nanostructures and ideal compositions in a massive production are highly cherished.On account of the reserve,low cost and diverse micro-nanostructures,silicate minerals are proposed as promising raw materials.In the article,crystal structures and the reduction approaches for silicate minerals,as well as recent progress on the as-reduced Si products for clean energy storage/conversion,are presented systematically.Moreover,some cutting-edge fields involving Si materials are discussed,which may offer deep insights into the rational design of advanced Si nanostructures for extended energy-related fields.展开更多
SBA-15(mesoporous SiO2) is used to stabilize and transfer F-in the NH4BF4 CVD reaction for the first time, and a large-scale crystalline h-BN phase can be prepared. We successfully fabricate hollow h-BN capsules wit...SBA-15(mesoporous SiO2) is used to stabilize and transfer F-in the NH4BF4 CVD reaction for the first time, and a large-scale crystalline h-BN phase can be prepared. We successfully fabricate hollow h-BN capsules with collapsed surfaces in our designed NH4BF4 CVD system. Optimum temperature conditions are obtained, and a detailed formation mechanism is further proposed. The successful SBA-15-assisted NH4BF4 CVD route is of importance and enriches the engineering technology in the h-BN single-source CVD reaction.展开更多
Visible light photocatalytic CO2 conversion is a promising solution to global warming and energy shortage.Herein,we build a well-designed bridge-like nanostructure,that is,the phosphonated Ru complex(RuP)light absorbe...Visible light photocatalytic CO2 conversion is a promising solution to global warming and energy shortage.Herein,we build a well-designed bridge-like nanostructure,that is,the phosphonated Ru complex(RuP)light absorber–TiO2 bridge–Cu catalyst.In this nanostructure,brookite TiO2 serving as a bridge is spatially connected to the RuP and Cu on each of its sides and could thus physically separate the photoexcited holes and electrons over the RuP and Cu,respectively.Given its eff ective charge separation,this RuP–TiO2–Cu assembly exhibits superior CO2 photoreduction activity relative to RuP–SiO2–Cu under visible light irradiation(λ>420 nm).The catalytic activity is further optimized by adopting brookite TiO2 with various electronic band structures.Results reveal the rapid movement of electrons from the RuP through the conduction band of TiO2 and fi nally to the Cu surface.This property is crucial in CO2 photoreduction activity.展开更多
CONSPECTUS:Nanoporous carbon(NPC)materials with various architectures have attracted considerable attention because of their distinctive properties and great application potential in environmental remediation,energy c...CONSPECTUS:Nanoporous carbon(NPC)materials with various architectures have attracted considerable attention because of their distinctive properties and great application potential in environmental remediation,energy conversion and storage,advanced sensors,and other applications.Traditional methods for the synthesis of NPCs,for example,the pyrolysis of natural products or polymers,template-assisted synthesis,and using deep-eutectic solvents,always involve toxic precursors and complex procedures,which greatly hinder further applications.Therefore,it is highly desirable to explore simple and feasible ways to prepare NPCs.Furthermore,to improve the performance and extend the application fields of NPCs,efficient strategies should be developed to regulate the components at the atomic level and construct multidimensional architectures.展开更多
To explore the natural resources as sustainable precursors offers a family of green materials.The use of bio-waste precursors especially the remaining from food processing is a scalable,highly abundant,and cost-effect...To explore the natural resources as sustainable precursors offers a family of green materials.The use of bio-waste precursors especially the remaining from food processing is a scalable,highly abundant,and cost-effective strategy.Exploring waste materials is highly important especially for new materials discovery in emerging energy storage technologies such as lithium sulfur batteries(LSBs).Herein,waste milk powder is carbonized and constructed as the sulfur host with the hollow micro-/mesoporous framework,and the resulting carbonized milk powder and sulfur(CMP/S) composites are employed as cathodes for LSBs.It is revealed that the hollow micro-/mesoporous CMP/S framework can not only accommodate the volume expansion but also endow smooth pathways for the fast diffusion of electrons and Li-ions,leading to both high capacity and long cycling stability.The CMP/S composite electrode with 56 wt% loaded sulfur exhibits a remarkable initial capacity of 1596 mAh g^(-1) at 0.1 C,corresponding to 95% of the theoretical capacity.Even at a rate of 1 C,it maintains a high capacity of 730 mAh g^(-1) with a capacity retention of 72.6% after 500 cycles,demonstrating a very low capacity fading of only 0.05% per cycle.Importantly,the Coulombic efficiency is always higher than 96%during all the cycles.The only used source material is expired waste milk powders in our proposal.We believe that this "trash to treasure" approach will open up a new way for the utilization of waste material as environmentally safe and high performance electrodes for advanced LSBs.展开更多
The effect of cold high pressure densification(CHPD)on anisotropy of the critical current density(Jc)in《in situ》single core binary and alloyed MgB2 tapes has been determined as a function of temperatures at 4.2 K,20...The effect of cold high pressure densification(CHPD)on anisotropy of the critical current density(Jc)in《in situ》single core binary and alloyed MgB2 tapes has been determined as a function of temperatures at 4.2 K,20 K and 25 K as well as at applied magnetic fields up to 19 T.The study includes binary and C4H6O5(malic acid)doped MgB2 tapes before and after CHPD.It is remarkable that the CHPD process not only improved the Jc values,in particular at the higher magnetic fields,but also decreased the anisotropy ratio,Г=JC^///JC^⊥In binary MgB2 tapes,the anisotropy factor F increases with higher aspect ratios,even after applying CHPD.In malic acid(C4H6O5)doped tapes,however,the application of CHPD leads only to small enhancements ofГ,even for higher aspect ratios.This is attributed to the higher carbon content in the MgB2 filaments,which in turn is a consequence of the reduced chemical reaction path in the densified filaments.At all applied field values,it was found that CHPD processed C4H6O5 doped tapes exhibit an almost isotropic behavior.This constitutes an advantage in view of industrial magnet applications using wires with square or slightly rectangular configuration.展开更多
Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or u...Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or unpaired electrons.Currently,commercial methane conversion is usually carried out in harsh conditions with enormous energy input.Photocatalytic partial oxidation of methane to liquid oxygenates(PPOMO)is a future-oriented technology towards realizing high efficiency and high selectivity under mild conditions.The selection of oxidant is crucial to the PPOMO performance.Hence,attentions are paid to the research progress of PPOMO with various oxidants(O_(2),H_(2)O,H_(2)O_(2)and other oxidants).Moreover,the activation of the selected oxidants is also highly emphasized.Meanwhile,we summarized the methane activation mechanisms focusing on the C-H bond that was broken mainly by·OH radical,O-specie or photogenerated hole(h+).Finally,the challenges and prospects in this subject are briefly discussed.展开更多
Photothermal ethanol steam reforming(ESR) is currently limited by low intrinsic activity and strong solar energy dissipation.Herein,we synthesized Fe single atoms supported on CeO_(2)(SA Fe-CeO_(2)) to exhibit excelle...Photothermal ethanol steam reforming(ESR) is currently limited by low intrinsic activity and strong solar energy dissipation.Herein,we synthesized Fe single atoms supported on CeO_(2)(SA Fe-CeO_(2)) to exhibit excellent low-temperature ESR activity with a hydrogen production rate of 512 mmol g^(-1)h^(-1) at 350℃,becuase of the high oxidation state of Fe single atoms to weaken the reaction barrier of ethanol decomposition.Furthermore,a heterostructure of SA Fe-CeO_(2) and Ti foil could eliminate 66% of infrared radiation via the size effect,thus achieving a 3.5 sun-driven temperature of 347℃.Consequently,the heterostructure of SA Fe-CeO_(2) and Ti foil shows a hydrogen generation rate of 984 mmol g^(-1)h^(-1) of ESR and 11.31% of solar-to-hydrogen energy conversion efficiency,which outperforms other photothermal ethanol-hydrogen production systems.This study provides a new path for designing active catalytic sites and trapping light energy of photothermal catalysts.展开更多
基金supported by the Japan Society for the Promotion of Science(JSPS)KAKENHI Grant Number JP22F22368。
文摘The development of clean and sustainable energy sources has received widespread interest in the past few decades due to the rolling energy demands while extenuating the rising tiers of greenhouse gases and environmental pollution.Due to their intermittent nature,these green and sustainable sources require appropriate energy storage systems.Amongst different energy storage technologies,electrochemical energy storage devices,particularly supercapacitors(SCs),have fascinated global attention for their utilization in electric vehicles,power supports,portable electronics,and many others application requiring electric energy devices for their operation.Thus,the growth of SCs in the commercial market has squeezed requirements,and further developments are obligatory for their effective industrialization.In the meantime,SCs also face technical complications and contests for their introduction in industrial settings because of their low energy density and high Levelized cost.The present study combines core strengths,weaknesses,opportunities,and threats(SWOT)analysis of SCs with new perspectives and recent ideas.The challenges and the future progressive prospects of SCs are also presented in detail.This review will afford consistent direction and new superhighways for the further development of SCs as standalone and complementary energy storage systems.
基金financial support from the Tangshan Talent Funding Project(A202202007)the National Natural Science Foundation of China(21703065)+3 种基金the Natural Science Foundation of Hebei Province(B2018209267)the World Premier International Research Center Initiative(WPI Initiative)on Materials Nanoarchitectonics(MANA),the MEXT(Japan)the Photoexcitonix Project in Hokkaido Universitythe JSPS KAKENHI(Grant Number JP18H02065)。
文摘Taking copper doped ZnS(ZnS:Cu)nanocrystals as the main body of photocatalyst,the influence of different base transition metal ions(M^(2+)=Ni^(2+),Co^(2+),Fe^(2+)and Cd^(2+))on photocatalytic CO_(2)reduction in inorganic reaction system is investigated.Confined single-atom Ni^(2+),Co^(2+),and Cd^(2+)sites were created via cation-exchange process and enhanced CO_(2)reduction,while Fe^(2+)suppressed the photocatalytic activity for both water and CO_(2)reduction.The modified ZnS:Cu photocatalysts(M/ZnS:Cu)demonstrated tunable product selectivity,with Ni^(2+)and Co^(2+)showing high selectivity for syngas production and Cd^(2+)displaying remarkable formate selectivity.DFT calculations indicated favorable H adsorption free energy on Ni^(2+)and Co^(2+)sites,promoting the hydrogen evolution reaction.The selectivity of CO_(2)reduction products was found to be sensitive to the initial intermediate adsorption states.*COOH formed on Ni^(2+)and Co^(2+)while*OCHO formed on Cd^(2+),favoring the production of CO and HCOOH as the main products,respectively.This work provides valuable insights for developing efficient solar-to-fuel platforms with controlled CO_(2)reduction selectivity.
基金the financial support from the National Natural Science Foundation of China(22005099)。
文摘Electrocatalytic conversion of carbon dioxide to high value-added chemicals is a promising method for solving the energy crisis and global warming.Electrochemical active metal-containing conjugated polymers have been widely studied for heterogeneous carbon dioxide reduction.In the present contribution,we designed and synthesized a stable cobalt phthalocyanine-based conjugated polymer,named CoPPc-TFPPy-CP,and also explored its electro-catalytic application in carbon dioxide reduction to liquid products in an aqueous solution.In the catalyst,cobalt phthalocyanine acts as building blocks connected with 1,3,6,8-tetrakis(4-formyl phenyl)pyrenes via imine-linkages,leading to mesoporous formation polymers with the pore size centered at 4.1nm.And the central co-balt atoms shifted to a higher oxidation state after condensation.With these chemical and structural natures,the catalyst displayed a remarkable electrocatalytic CO_(2) reduction performance with an ethanol Faradaic efficiency of 43.25%at-1.0V vs RHE.While at the same time,the electrochemical reduction process catalyzed by cobalt phthalocyanine produced only carbon monoxide and hydrogen.To the best of our knowledge,CoPPc-TFPPy-CP is the first example among organic polymers and metal-organic frameworks that produces ethanol from CO_(2) with a remarkable selectivity.
基金financial support of International Center for Young Scientists(ICYS)World Premier International Center for Materials Nanoarchitectonics(WPI-MANA) in National Institute for Materials Science(NIMS)financial support from KAKENHI project(Grant-in-Aid for Young Scientists,26820322) of Japan Society for the Promotion of Science(JSPS)
文摘Boron nitride(BN) nanostructures with complementary functions to their carbon counterparts are one of the most intriguing nanomaterials.Here we devote a compact review on the syntheses of BN nanomaterials:typical zero-dimensional(OD) fullerenes and nanoparticles,one-dimensional(1D) nanotubes and nanoribbons,two-dimensional(2D) nanosheets as well as three-dimensional(3D) nanoporous BN.Combining low-dimensional quantum confinement and surface effects with unique physical and chemical properties of BN,e.g.excellent electric insulation,wide band gap,and high chemical and thermal stability,BN nanomaterials have drawn particular attention in a variety of potential applications,e.g.luminescence,functional composites,hydrogen accumulators,and advanced insulators,which are also reviewed.
基金supported in part by the WPIMANA,Ministry of Education,Culture,Sports,Science and TechnologyCREST of the Japan Science and Technology Agency(JST)(Grant No.JPMJCR17N1)the support from JSPS KAKENNHI grant 15H02004 and 18H03869.
文摘Layered double hydroxides(LDHs)have attracted tremendous research interest in widely spreading applications.Most notably,transition-metal-bearing LDHs are expected to serve as highly active electrocatalysts for oxygen evolution reaction(OER)due to their layered structure combined with versatile com-positions.Furthermore,reducing the thickness of platelet LDH crystals to nanometer or even molecular scale via cleavage or delamination provides an important clue to enhance the activity.In this review,recent progresses on rational design of LDH nanosheets are reviewed,including direct synthesis via traditional coprecipitation,homogeneous precipitation,and newly developed topochemical oxidation as well as chemical exfoliation of parent LDH crystals.In addition,diverse strategies are introduced to modulate their electrochemical activity by tuning the composition of host metal cations and intercalated counter-anions,and incorporating dopants,cavi-ties,and single atoms.In particular,hybridizing LDHs with conductive components or in situ growing them on conductive substrates to produce freestanding electrodes can further enhance their intrinsic catalytic activity.A brief discussion on future research directions and prospects is also summarized.
基金supported by the National Natural Science Foundation of China(Grant Nos.21505050,51672109)the Dispatch of Faculty Abroad of the University of Jinan+2 种基金the Natural Science Foundation of Shandong Province(Grant No.ZR2016FM30)supported in part by the WPI-MANA,Ministry of Education,Culture,Sports,Science and Technology,Japansupport from JSPS KAKENNHI(18H03869)
文摘Layered double hydroxides (LDHs), a class of anionic clays consisting of brucite-like host layers and interlayer anions, have been widely investigated in the last decade due to their promising applications in many areas such as catalysis, ion separation and adsorption. Owing to the highly tunable compositi on and uniform distribution of metal cations in the brucite-like layers, as well as the facile exchangeability of intercalated anions, LDHs can be modified and functionalized to form various nanostructures/composites through versatile processes such as anion intercalation and exfoliation, decoration of nanoparticles, selfassembly with other two-dimensional (2D) materials, and controlled growth on conductive supports (e.g., nanowire arrays, nano tubes, 3D foams). In this article, we briefly review the recent advances on both the LDH nano structures and functionalized composites toward the applications in energy conversion, especially for water oxidation.
基金National Natural Science Foundation of China,Grant/Award Numbers:51874357,51872333,U20A20123。
文摘The lattice-oxygen-mediated mechanism is considered as a reasonable mechanism for the electrochemical catalytic oxygen evolution reaction(OER)of NiFe layered double hydroxides(LDHs).A NiFe LDH with distinct lattice contraction and microcrystallization was synthesized via a simple one-step method using sodium gluconate.The lattice contraction is attributed to the interaction of carbon in sodium gluconate and iron in NiFe LDH.The NiFe LDH with optimized microcrystallization and lattice contraction shows a low overpotential of 217 mV at a current density of 10 mA cm^(−2) and excellent durability of 20 h at a high current density of 100 mA cm^(−2).The results revealed that a contractive metal–oxygen bond could boost the intrinsic activity of active sites and the microcrystallization promotes an increase in the number of active sites in terms of unit area.The chemical environment of oxygen elemental characterization and resistance at different chronopotentiometry times confirm that the lattice oxygen element is indeed involved in the process of OER,supporting the lattice-oxygen-mediated mechanism of NiFe LDH.Density functional theory calculations reveal that contractive metal–oxygen bonds induced a reduction of the adsorption energy barrier of intermediate products,thus improving the intrinsic catalytic activity.The special characteristics of microcrystallization and lattice contraction of NiFe LDH provide a strategy to improve both the number and the intrinsic activity of active sites in a versatile manner.
基金supported by the Ministry of Education,Culture,Sports,Science and Technology(MEXT) through Grants-in-Aid for Scientific Research(Grant Nos.24241040 and 25110008)the World Premier International Research Center Initiative(WPI),MEXT,Japan
文摘√√The electronic structures of monolayer silicenes(4 × 4 and■ ×■R13.9o) grown on Ag(111) surface are studied by scanning tunneling spectroscopy(STS) and density functional theory(DFT) calculations. While both phases have similar electronic structures around the Fermi level, significant differences are observed in the higher energy unoccupied states.The DFT calculations show that the contributions of Si 3pz orbitals to the unoccupied states are different because of their different buckled configurations.
基金financially supported by JSPS KAKENHI(JP18H02065)Photo-excitonic Project in Hokkaido University,National Natural Science Foundation of China(21633004,22002060,and 51872138)+4 种基金Natural Science Foundation of Jiangsu Province(BK20181380)Qing Lan Project,Six Talent Peaks Project in Jiangsu Province(XCL-029)Priority Academic Program Development of the Jiangsu Higher Education Institutions(PAPD)the support provided by the China Scholarships Council(202008320109)China Postdoctoral Science Foundation(2020M681564)。
文摘Photocatalytic conversion of CO_(2)into solar fuels provides a bright route for the green and sustainable development of human society.However,the realization of efficient photocatalytic CO_(2)reduction reaction(CO_(2)RR)is still challenging owing to the sluggish kinetics or unfavorable thermodynamics for basic chemical processes of CO_(2)RR,such as adsorption,activation,conversion and product desorption.To overcome these shortcomings,recent works have demonstrated that surface engineering of semiconductors,such as introducing surface vacancy,surface doping,and cocatalyst loading,serves as effective or promising strategies for improved photocatalytic CO_(2)RR with high activity and selectivity.The essential reason lies in the activation and reaction pathways can be optimized and regulated through the reconstruction of surface atomic and electronic structures.Herein,in this review,we focus on recent research advances about rational design of semiconductor surface for photocatalytic CO_(2)RR.The surface engineering strategies for improved CO_(2)adsorption,activation,and product selectivity will be reviewed.In addition,theoretical calculations along with in situ characterization techniques will be in the spotlight to clarify the kinetics and thermodynamics of the reaction process.The aim of this review is to provide deep understanding and rational guidance on the design of semiconductors for photocatalytic CO_(2)RR.
基金China Postdoctoral Science Foundation,Grant/Award Number:2019M661825Natural Science Foundation of Jiangsu Province,Grant/Award Numbers:BK20190413,BK20210616Japan Society。
文摘Aprotic lithium–oxygen batteries(LOBs)have been recognized as novel energy storage devices for their outstanding specific energy density,while the large discharge/charge overpotential is a tough barrier to be overcome.Here,hetero-structured MoS_(2)/ZnIn_(2)S_(4) nanosheets have been prepared to capture visible light and the generated charge carriers are utilized for promoting both the oxygen reduction reaction and the oxygen evolution reaction.With the light illumination in the discharge process,the abundant photo-inspired electrons serve as the reaction sites to promote the reduction of O_(2) into LiO_(2) which is finally deposited as Li_(2)O_(2).On the contrary,the generated holes in the valence band can contribute to the low oxidization potential of Li_(2)O_(2) during the charge process.It delivers a low charge potential of 3.29 V,with an excellent resulting energy efficiency of 96.7%,much superior to that of 69.2%in the dark condition.It is noted that the involvement of photoelectrons has influenced the growth of Li_(2)O_(2) films on the MoS_(2)/ZnIn_(2)S_(4) nanosheets through the surface-adsorption pathway.The insights from the theoretical calculation confirm that the photoelectrons favor the absorption of LiO_(2) and the formation of the Li_(2)O_(2) film through the surface route.Therefore,this paper provides a deeper understanding of the mechanism of photoinspired charge carriers in LOBs and will enable further exploration of photo-involved energy storage systems.
基金the financial support by the National Natural Science Foundation of China(51874357,51872333,U20A20123)Innovative Research Group of Hunan Provincial Natural Science Foundation of China(2019JJ10006)support from Shenghua Scholar Program of Central South University.R.M.acknowledges support from JSPS KAKENNHI(18H03869)。
文摘Strategy of anchoring alloy nanoparticles made up of the efficient catalytic element(e.g.,Ni,Fe)on dodecyl sulfate(DS^(-))-intercalated NiFe layered double hydroxides(DS^(-)-NiFe LDH)obtained by a convenient one-step hydrothermal coprecipitation method for essentially enhancing oxygen evolution reaction(OER)performance was proposed.The results of structural characterization indicate Pt_(2)FeNi alloy nanoparticles evenly distribute on the surface of DS^(-)-NiFe LDH.The sizes of the Pt_(2)FeNi nanoparticles,closely related to their OER performance,could be wellcontrolled by adjusting the amount of H;PtCl;addition.The composite structure of as-prepared product was stable during processes of synthesis,exfoliation,self-assembly,and subsequent electrocatalytic OER.Rigorous electrochemical test proving the contributing catalytic active sites was located at the interface between Pt_(2)FeNi and DS^(-)-NiFe LDH,and the Ni and Fe were the major active elements while O atoms are adsorption sites.The formation of Pt_(2)FeNi nanoparticles could greatly prompt the reduction of Tafel slope.The best-performing Pt_(2)FeNi/DS^(-)-NiFe LDH with a Pt content of 0.98 wt%achieved low overpotential of 204 mV at 10 mA cm^(-2)and 262 mV at 50 mA cm^(-2).This work provides a convenient and effective strategy to create additional active sites for enhancing OER performance of NiFe LDH and make contribution to its wide application.
基金the Queensland Government for Advance Queensland Research Fellowship in partnership with Siemens Energy(Aust)Pty Ltd and QUT which partially supported this workby the Australian Research Council,Australia(Grant No.LP160101784)。
文摘Low activation isotopic boron(11B)based magnesium diboride(Mg^(11)B_(2))superconductors doped with biomass-derived activated carbon were synthesized using11B and magnesium powder via solid-state reaction.The effect of carbon doping on the lattice structure and superconducting properties of Mg^(11)B_(2)bulks were evaluated using X-ray powder diffraction,high resolution transmission electron microscopy,scanning electron microscopy and magnetization measurements.Precise refinement of structural parameters indicates successful substitution of carbon in Mg^(11)B_(2)bulks.The critical current density(Jc)of carbon doped Mg^(11)B_(2)synthesized at 650℃was enhanced more than two times compared with the pure Mg^(11)B_(2)bulk.Similar improvement was observed for the Mg^(11)B_(2)bulks heat-treated at 800℃.This enhancement is due to successful substitution of biomass-derived carbon with high surface area into Mg^(11)B_(2)lattice.The flux pinning mechanism of pure and doped Mg^(11)B_(2)bulks were investigated using the Dew-Hughes model.This study provides information regarding enhancement of the Jc of low activation Mg^(11)B_(2)superconductors suitable for next-generation fusion magnets.
基金financially supported by National Natural Science Foundation of China(51702291,51874357,U20A20123)the China Postdoctoral Science Foundation(2020M682352)+1 种基金State Key Laboratory of Powder Metallurgy,Central South University,Changsha,Chinasupport from the Youth Talent Program of Zhengzhou University and Henan Provincial Key Technology R&D Program(212102210597)。
文摘To effectively alleviate the ever-increasing energy crisis and environmental issues,clean and sustainable energy-related materials as well as the corresponding storage/conversion devices are in urgent demand.Silicon(Si) with the second most elemental abundance on the crust in the form of silicate or silica(SiO_(2)) minerals,is an advanced emerging material showing high performance in energy-related fields(e.g.batteries,photocatalytic hydrogen evolution).For the improved performance in industry-scale applications,Si materials with delicate nanostructures and ideal compositions in a massive production are highly cherished.On account of the reserve,low cost and diverse micro-nanostructures,silicate minerals are proposed as promising raw materials.In the article,crystal structures and the reduction approaches for silicate minerals,as well as recent progress on the as-reduced Si products for clean energy storage/conversion,are presented systematically.Moreover,some cutting-edge fields involving Si materials are discussed,which may offer deep insights into the rational design of advanced Si nanostructures for extended energy-related fields.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51332005,51372066,51172060,51202055,and 21103056)
文摘SBA-15(mesoporous SiO2) is used to stabilize and transfer F-in the NH4BF4 CVD reaction for the first time, and a large-scale crystalline h-BN phase can be prepared. We successfully fabricate hollow h-BN capsules with collapsed surfaces in our designed NH4BF4 CVD system. Optimum temperature conditions are obtained, and a detailed formation mechanism is further proposed. The successful SBA-15-assisted NH4BF4 CVD route is of importance and enriches the engineering technology in the h-BN single-source CVD reaction.
基金This work received fi nancial support from the National Natural Science Foundation of China(No.21633004).
文摘Visible light photocatalytic CO2 conversion is a promising solution to global warming and energy shortage.Herein,we build a well-designed bridge-like nanostructure,that is,the phosphonated Ru complex(RuP)light absorber–TiO2 bridge–Cu catalyst.In this nanostructure,brookite TiO2 serving as a bridge is spatially connected to the RuP and Cu on each of its sides and could thus physically separate the photoexcited holes and electrons over the RuP and Cu,respectively.Given its eff ective charge separation,this RuP–TiO2–Cu assembly exhibits superior CO2 photoreduction activity relative to RuP–SiO2–Cu under visible light irradiation(λ>420 nm).The catalytic activity is further optimized by adopting brookite TiO2 with various electronic band structures.Results reveal the rapid movement of electrons from the RuP through the conduction band of TiO2 and fi nally to the Cu surface.This property is crucial in CO2 photoreduction activity.
基金This work was financially supported by the National Key Research and Development Program of China(no.2019YFC0408302)the National Natural Science Foundation of China(no.51878352)+4 种基金the JST-ERATO Yamauchi Materials Space-Tectonics Project(JPMJER2003)C.W.acknowledges the support of the Initiative Postdocs Supporting Program(BX20200167)the China Postdoctoral Science Foundation(no.2020M680070)This work was also performed in part at the Queensland node of the Australian National Fabrication Facility(ANFF-Q)a company established under the National Collaborative Research Infrastructure Strategy to provide nano-and microfabrication facilities for Australian researchers.
文摘CONSPECTUS:Nanoporous carbon(NPC)materials with various architectures have attracted considerable attention because of their distinctive properties and great application potential in environmental remediation,energy conversion and storage,advanced sensors,and other applications.Traditional methods for the synthesis of NPCs,for example,the pyrolysis of natural products or polymers,template-assisted synthesis,and using deep-eutectic solvents,always involve toxic precursors and complex procedures,which greatly hinder further applications.Therefore,it is highly desirable to explore simple and feasible ways to prepare NPCs.Furthermore,to improve the performance and extend the application fields of NPCs,efficient strategies should be developed to regulate the components at the atomic level and construct multidimensional architectures.
基金supported by Innovation Platform of Energy Storage Engineering and New Material in Zhejiang University (K19-534202-002)Provincial Innovation Team on Hydrogen Electric Hybrid Power Systems in Zhejiang ProvinceShenzhen Science and Technology Project (JCYJ20170412105400428)。
文摘To explore the natural resources as sustainable precursors offers a family of green materials.The use of bio-waste precursors especially the remaining from food processing is a scalable,highly abundant,and cost-effective strategy.Exploring waste materials is highly important especially for new materials discovery in emerging energy storage technologies such as lithium sulfur batteries(LSBs).Herein,waste milk powder is carbonized and constructed as the sulfur host with the hollow micro-/mesoporous framework,and the resulting carbonized milk powder and sulfur(CMP/S) composites are employed as cathodes for LSBs.It is revealed that the hollow micro-/mesoporous CMP/S framework can not only accommodate the volume expansion but also endow smooth pathways for the fast diffusion of electrons and Li-ions,leading to both high capacity and long cycling stability.The CMP/S composite electrode with 56 wt% loaded sulfur exhibits a remarkable initial capacity of 1596 mAh g^(-1) at 0.1 C,corresponding to 95% of the theoretical capacity.Even at a rate of 1 C,it maintains a high capacity of 730 mAh g^(-1) with a capacity retention of 72.6% after 500 cycles,demonstrating a very low capacity fading of only 0.05% per cycle.Importantly,the Coulombic efficiency is always higher than 96%during all the cycles.The only used source material is expired waste milk powders in our proposal.We believe that this "trash to treasure" approach will open up a new way for the utilization of waste material as environmentally safe and high performance electrodes for advanced LSBs.
基金This work was supported by the Australian Research Council(Grant No.LP160101784)A.K.thanks the Researchers Supporting Project(RSP-2019/127)King Saud University,Riyadh,Saudi Arabia for the support.This work was performed in part at the Queensland node of the Australian National Fabrication Facility,a company established under the National Collaborative Research Infrastructure Strategy to provide nano-and microfabrication facilities for Australia's researchers.M.M.acknowledges an internal funding project of the University of Osijek(ZUP-2018).
文摘The effect of cold high pressure densification(CHPD)on anisotropy of the critical current density(Jc)in《in situ》single core binary and alloyed MgB2 tapes has been determined as a function of temperatures at 4.2 K,20 K and 25 K as well as at applied magnetic fields up to 19 T.The study includes binary and C4H6O5(malic acid)doped MgB2 tapes before and after CHPD.It is remarkable that the CHPD process not only improved the Jc values,in particular at the higher magnetic fields,but also decreased the anisotropy ratio,Г=JC^///JC^⊥In binary MgB2 tapes,the anisotropy factor F increases with higher aspect ratios,even after applying CHPD.In malic acid(C4H6O5)doped tapes,however,the application of CHPD leads only to small enhancements ofГ,even for higher aspect ratios.This is attributed to the higher carbon content in the MgB2 filaments,which in turn is a consequence of the reduced chemical reaction path in the densified filaments.At all applied field values,it was found that CHPD processed C4H6O5 doped tapes exhibit an almost isotropic behavior.This constitutes an advantage in view of industrial magnet applications using wires with square or slightly rectangular configuration.
基金the National Key R&D Program of China(No.2021YFA1500800)National Natural Science Foundation of China(No.22072106).
文摘Methane chemistry is one of the“Holy Grails of catalysis”.It is highly desirable but challenge to transform methane into value-added chemicals,because of its high C-H bonding energy(435 kJ/mol),lack ofπbonding or unpaired electrons.Currently,commercial methane conversion is usually carried out in harsh conditions with enormous energy input.Photocatalytic partial oxidation of methane to liquid oxygenates(PPOMO)is a future-oriented technology towards realizing high efficiency and high selectivity under mild conditions.The selection of oxidant is crucial to the PPOMO performance.Hence,attentions are paid to the research progress of PPOMO with various oxidants(O_(2),H_(2)O,H_(2)O_(2)and other oxidants).Moreover,the activation of the selected oxidants is also highly emphasized.Meanwhile,we summarized the methane activation mechanisms focusing on the C-H bond that was broken mainly by·OH radical,O-specie or photogenerated hole(h+).Finally,the challenges and prospects in this subject are briefly discussed.
基金supported by the National Natural Science Foundation of China(Grant No.52371220)Natural Science Foundation of Hebei Province(Grant Nos.B2023204034,B2023201107,B2022201090,B2021201074,B2021201034,F2021203097)+5 种基金Hebei Provincial Department of Science and Technology(Grant No.216Z4303G)Hebei Education Department(Grant No,QN2022059)Interdisciplinary Research Program of Natural Science of Hebei University(Grant Nos.521100311,DXK202109)the Advanced Talents Incubation Program of Hebei University(Grant Nos.521100223213,521000981248,521000981377 and 8012605)Hebei University(050001-521100302025,050001-513300201004)the Scientific Research Foundation of Hebei Agricultural University(YJ201939)。
文摘Photothermal ethanol steam reforming(ESR) is currently limited by low intrinsic activity and strong solar energy dissipation.Herein,we synthesized Fe single atoms supported on CeO_(2)(SA Fe-CeO_(2)) to exhibit excellent low-temperature ESR activity with a hydrogen production rate of 512 mmol g^(-1)h^(-1) at 350℃,becuase of the high oxidation state of Fe single atoms to weaken the reaction barrier of ethanol decomposition.Furthermore,a heterostructure of SA Fe-CeO_(2) and Ti foil could eliminate 66% of infrared radiation via the size effect,thus achieving a 3.5 sun-driven temperature of 347℃.Consequently,the heterostructure of SA Fe-CeO_(2) and Ti foil shows a hydrogen generation rate of 984 mmol g^(-1)h^(-1) of ESR and 11.31% of solar-to-hydrogen energy conversion efficiency,which outperforms other photothermal ethanol-hydrogen production systems.This study provides a new path for designing active catalytic sites and trapping light energy of photothermal catalysts.