Research progress of precise structural regulation of single atom catalyst for accelerating electrocatalytic oxygen reduction reaction

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.

Charge-transfer-regulated bimetal ferrocene-based organic frameworks for promoting electrocatalytic oxygen evolution

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.

In situ confined vertical growth of Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)nanoarrays on rGO for an efficient oxygen evolution reaction

Rational design of oxygen evolution reaction(OER)catalysts at low cost would greatly benefit the economy.Taking advantage of earth-abundant elements Si,Co and Ni,we produce a unique-structure where cobalt-nickel silicate hydroxide[Co_(2.5)Ni_(0.5)Si_(2)O_(5)(OH)_(4)]is vertically grown on a reduced graphene oxide(rGO)support(CNS@rGO).This is developed as a low-cost and prospective OER catalyst.Compared to cobalt or nickel silicate hydroxide@rGO(CS@rGO and NS@rGO,respectively)nanoarrays,the bimetal CNS@rGO nanoarray exhibits impressive OER performance with an overpotential of 307 mV@10 mA cm^(-2).This value is higher than that of CS@rGO and NS@rGO.The CNS@rGO nanoarray has an overpotential of 446 mV@100 mA cm^(-2),about 1.4 times that of the commercial RuO_(2)electrocatalyst.The achieved OER activity is superior to the state-of-the-art metal oxides/hydroxides and their derivatives.The vertically grown nanostructure and optimized metal-support electronic interactions play an indispensable role for OER performance improvement,including a fast electron transfer pathway,short proton/electron diffusion distance,more active metal centers,as well as optimized dualatomic electron density.Taking advantage of interlay chemical regulation and the in-situ growth method,the advanced-structural CNS@rGO nanoarrays provide a new horizon to the rational and flexible design of efficient and promising OER electrocatalysts.

Electronic modulation of two-dimensional bismuth-based nanosheets for electrocatalytic CO_(2) reduction to formate: A review

Electrocatalytic CO_(2) reduction reaction(eCO_(2) RR)has significant relevance to settle the global energy crisis and abnormal climate problem via mitigating the excess emission of waste CO_(2) and producing high-value-added chemicals.Currently,eCO_(2) RR to formic acid or formate is one of the most technologically and economically viable approaches to realize high-efficiency CO_(2) utilization,and the development of efficient electrocatalysts is very urgent to achieve efficient and stable catalytic performance.In this review,the recent advances for two-dimensional bismuth-based nanosheets(2D Bi-based NSs)electrocatalysts are concluded from both theoretical and experimental perspectives.Firstly,the preparation strategies of 2D Bi-based NSs in aspects to precisely control the thickness and uniformity are summarized.In addition,the electronic regulation strategies of 2D Bi-based NSs are highlighted to gain insight into the effects of the structure-property relationship on facilitating CO_(2) activation,improving product selectivity,and optimizing carrier transport dynamics.Finally,the considerable challenges and opportunities of 2D Bi-based NSs are discussed to lighten new directions for future research of eCO_(2) RR.

Single-cluster electronics using metallic clusters:Fabrications,regulations,and applications

Metallic clusters,ranging from 1 to 2 nm in size,have emerged as promising candidates for creating nanoelectronic devices at the single-cluster level.With the intermediate quantum properties between metals and semiconductors,these metallic clusters offer an alternative pathway to silicon-based electronics and organic molecules for miniaturized electronics with dimensions below 5 nm.Significant progress has been made in studies of single-cluster electronic devices.However,a clear guide for selecting,synthesizing,and fabricating functional single-cluster electronic devices is still required.This review article provides a comprehensive overview of single-cluster electronic devices,including the mechanisms of electron transport,the fabrication of devices,and the regulations of electron transport properties.Furthermore,we discuss the challenges and future directions for single-cluster electronic devices and their potential applications.

The recent progress of pitch-based carbon anodes in sodium-ion batteries

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.

Recent Progress and Prospects of Layered Cathode Materials for Potassium-ion Batteries

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).

Synthesis,Crystal Structure and Plant Growth Regulatory Activity of 1-(3-Amino-[1,2,4]triazol-1-yl)-3,3-dimethyl-butan-2-one

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.

Structural regulation of single-atom catalysts for enhanced catalytic oxidation performance of volatile organic compounds

The catalytic oxidation of volatile organic compounds(VOCs)is considered a feasible method for VOCs treatment by virtue of its low technical cost,high economic efficiency,and low additionally produced pollutants,which is of important social value.Singleatom catalysts(SACs)with 100%atom utilization and uniform active sites usually have high activity and high product selectivity,and promise a broad range of applications.Precise regulation of the microstructures of SACs by means of defect engineering,interface engineering,and electronic effects can further improve the catalytic performance of VOCs oxidation.In this review,we introduce the mechanisms of VOCs oxidation,and systematically summarize the recent research progress of SACs in catalytic VOCs total oxidation into CO_(2)and H_(2)O,and then discuss the effects of various structural regulation strategies on the catalytic performance.Finally,we summarize the current problems yet to be solved and challenges currently faced in this field,and propose future design and research ideas for SACs in catalytic oxidation of VOCs.

Construction of N-doped carbon frames anchored with Co single atoms and Co nanoparticles as robust electrocatalyst for hydrogen evolution in the entire pH range

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.

Structural regulation of single-atomic site catalysts for enhanced electrocatalytic CO_(2)reduction

Electrocatalytic CO_(2)reduction reaction(CO_(2)RR)is considered an efficient way to convert CO_(2)into high-value-added chemicals,and thus is of significant social and economic value.Metal single-atomic site catalysts(SASCs)generally have excellent selectivity because of their 100%atomic utilization and uniform structure of active sites,and thus promise a broad range of applications.However,SASCs still face challenges such as low intrinsic activity and low density of active sites.Precise regulation of the microstructures of SASCs is an effective method to improve their CO_(2)RR performance and to obtain deep reduction products.In this article,we systematically summarize the current research status of SASCs developed for highly efficient catalysis of CO_(2)RR,discuss the various structural regulation methods for enhanced activity and selectivity of SASCs for CO_(2)RR,and review the application of in-situ characterization technologies in the SASC-catalyzed CO_(2)RR.We then discuss the problems yet to be solved in this area,and propose the future directions of the research on the design and application of SASCs for CO_(2)RR.

Synthesis of Highly Luminescent LnMOFs through Structural Regulation

Two series of three dimensional(3D)lanthanide metal-organic frameworks(LnMOFs)of[Ln(tftpa)1.5(phen)(H_(2)O)]_(n)(Ln=Sm 1a,Eu 1b,Tb 1c,Dy 1d,H2tftpa=tetrafluoroterephthalic acid,phen=1,10-phenanthrolin)and[Ln(tftpa)1.5(bpy)(H_(2)O)]_(n)(Ln=Sm 2a,Eu 2b,Tb 2c,Dy 2d,bpy=2,2'-bipyridine)are obtained by structural regulation.Results reveal that the 3D LnMOFs show high water-and thermal-stability.Interestingly,through selecting the perfluorinated ligand,and using bpy as an auxiliary ligand to hold back the solvents near to the lanthanide ions,2b,and 2c show high luminescence quantum yield(QY)of 74.50%and 60.03%,respectively.In order to further improve the luminescence QY,the auxiliary ligand of phen with larger conjugation and more rigid structure is synthesized to replace bpy,and fortunately,higher luminescence QY of 80.73%(1b)and 75.17%(1c)are realized.

Delicate synthesis of quasi-inverse opal structural Na_(3)V_(2)(PO_(4))_(3)/N-C and Na4MnV(PO_(4))_(3)/N-C as cathode for high-rate sodium-ion batteries

Poor conductivity and sluggish Na^(+) diffusion kinetic are two major drawbacks for practical application of sodium super-ionic conductor(NASICON) in sodium-ion batteries. In this work, we report a simple approach to synthesize quasi-inverse opal structural NASICON/N-doped carbon for the first time by a delicate one-pot solution-freeze drying-calcination process, aiming at fostering the overall electrochemical performance. Especially, the quasi-inverse opal structural Na_(3)V_(2)(PO_(4))_(3)/N-C(Q-NVP/N-C) displayed continuous pores, which provides interconnected channels for electrolyte permeation and abundant contacting interfaces between electrolyte and materials, resulting in faster kinetics of redox reaction and higher proportion of capacitive behavior.As a cathode material for sodium-ion batteries, the Q-NVP/N-C exhibits high specific capacity of 115 mAh·g^(-1) at 1C, still 61 mAh·g^(-1) at ultra-high current density of 100C,and a specific capacity of 89.7mAh·g^(-1) after 2000 cycles at 20C.This work displays the general validity of preparation method for not only Q-NVP/N-C,but also Na_(3)V_(2)(PO_(4))_(3),which provides a prospect for delicate synthesis of NASICON materials with excellent electrochemical performance.

Structural regulation strategies towards high performance organic materials for next generation aqueous Zn-based batteries

Environmental degradation has promoted the exploitation of novel energy-storage devices.Electrochemical en-ergy technologies,including supercapacitors and aqueous batteries,are highly desirable for energy storage appli-cations.Among them,aqueous zinc-based batteries(AZBs)are highly valued because of their inherent safety and low cost.One class of emerging materials favorably employed in these devices are organic cathodes,featuring resource renewability,cost-effectiveness,and adjustable electrochemical properties via facile structural modi-fication compared to the conventional inorganic cathodes.To date,various types of organic compounds have been developed and applied to AZBs.This paper comprehensively reviews the mechanisms involved in organic electrode material reactions,highlighting the structural modifications,including morphological,molecular,func-tional group,crystal,and electronic structures,affecting the final device performance.Conclusively,the prospects of practical applications of zinc/organic aqueous battery are delineated.

Modulate the electronic structure of Cu_(7)S_(4)nanosheet on TiO_(2)for enhanced photocatalytic hydrogen evolution

TiO_(2)is a promising photocatalyst due to its high thermodynamic stability and non-toxicity.However,its applications have been still limited because of the high recombination rate of electron-hole pairs.Herein,we show that by combining heterojunction construction and electronic structure regulation,the electron-hole pairs in TiO_(2)can be effectively separated for enhanced photocatalytic hydrogen evolution.The optimized Cu_(7)S_(4)nanosheet decorated TiO_(2)achieves much enhanced H_(2)evolution rate(11.5 mmol·g−1·h−1),which is 13.8 and 4.2 times of that of TiO_(2)and Cu_(7)S_(4)/TiO_(2),respectively.The results of photoluminescence spectroscopy,transient photocurrent spectra,ultraviolet-visible diffuse reflectance spectra,and electrochemical impedance spectroscopy collectively demonstrate that the enhanced photocatalytic performance of Air-Cu_(7)S_(4)/TiO_(2)is attributed to the effective separation of charge carriers and widened photoresponse range.The electron paramagnetic resonance and X-ray photoelectron spectroscopy results indicate that the increase of Cu2+in the Cu_(7)S_(4)nanosheet after calcination can promote the charge transfer.This work provides an effective method to improve the electron migration rate and charge separation of TiO_(2),which holds great significance for being extended to other material systems and beyond.

Regulating electronic structure of CoN_(4)with axial Co-S for promoting oxygen reduction and Zn-air battery performance

Regulating the coordination environment of transition-metal based materials in the axial direction with heteroatoms has shown great potential in boosting the oxygen reduction reaction(ORR).The coordination configuration and the regulation method are pivotal and elusive.Here,we report a combined strategy of matrix-activization and controlled-induction to modify the CoN_(4)site by axial coordination of Co-S(Co1N_(4)-S_(1)),which was validated by the aberration-corrected electron microscopy and X-ray absorption fine structure analysis.The optimal Co1N_(4)-S_(1)exhibits an excellent alkaline ORR activity,according to the half-wave potential(0.897 V vs.reversible hydrogen electrode(RHE)),Tafel slope(24.67 mV/dec),and kinetic current density.Moreover,the Co1N_(4)-S_(1)based Zn-air battery displays a high power density of 187.55 mW/cm^(2)and an outstanding charge-discharge cycling stability for 160 h,demonstrating the promising application potential.Theoretical calculations indicate that the better regulation of CoN_(4)on electronic structure and thus the highly efficient ORR performance can be achieved by axial Co-S.

The promoting effect of interstitial hydrogen on the oxygen reduction performance of PtPd alloy nanotubes for fuel cells

Highly efficient and stable oxygen reduction reaction(ORR)electrocatalysts are remarkably important but challenging for advancing the large-scale commercialization of practical proton exchange membrane fuel cells(PEMFCs).In this work,we report that the introduction of interstitial hydrogen atoms into PtPd nanotubes can significantly promote ORR performance without scarifying the durability.The enhanced mass activity was 8.8 times higher than that of commercial Pt/C.The accelerated durability test showed negligible activity attenuation after 30,000 cycles.Additionally,H2/O2 fuel cell tests further verified the excellent activity of PtPd-H nanotubes with a maximum power density of 1.32 W·cm^(−2),superior to that of commercial Pt/C(1.16 W·cm^(−2)).Density functional theory calculations demonstrated the incorporation of hydrogen atoms gives rise to the broadening of Pt d-band and the downshift of d-band center,which consequently leads to the weaker intermediates binding and enhanced ORR activity.

Metal sulfides based composites as promising efficient microwave absorption materials:A review

The increasingly severe electromagnetic microwave pollution raises higher requirements for the development of efficient microwave absorption(MA)materials.Metal sulfides are regarded as potential robust MA materials because of their unique optical,thermal,electrical,and magnetic properties,as well as the controllable microstructures.However,due to the limited MA performances of unary metal sulfides,morphology regulations and foreign materials hybridizations are adopted as effective strategies to improve their MA performances.Recent years witnessed the fast research progresses on the metal sulfides based MA materials and thus,a systematic literature survey on the materials design,fabrication,characterizations,MA behaviors,and the mechanisms behind is,highly desirable to summarize the rapid progress of this hot research area so as to provide guidance for the future development trend.This review firstly reviewed the research background,research progress,and basic principles of MA materials.Subsequently,the present synthetic methods and performance improvement strategies of metal sulfides based MA materials are systematically introduced.Then,by comparing the MA properties of one-dimensional,two-dimensional,and three-dimensional metal sulfides based composites,the influence of dimensionality and morphology on the MA properties are analyzed.By summarizing the research process of metal sulfides/dielectrics composites,metal sulfides/magnets composites,and metal sulfides/dielectrics/magnets composites MA materials,the influence of foreign materials hybridizations on the loss mechanisms and impedance matching conditions of metal sulfides based composites are revealed.Finally,the challenges and development prospects of metal sulfides based MA materials are presented.This review would provide a comprehensive understanding and insightful guidance for the exploration and development of efficient MA materials with thin thickness,light weight,wide absorption bandwidth,and strong absorption intensity.

Progress in graphene-based magnetic hybrids towards highly efficiency for microwave absorption

Nowadays, the yearning for microwave absorption materials(MAMs) are more and more urgent for dealing with the increasingly serious electromagnetic pollution and the demand of modern military security.Among potential candidates, the graphene(GE) based magnetic hybrids have advantages in structural controllable and designing flexibility, providing opportunities for achieving highly efficiency of microwave absorption(MA). Thus, the structural regulation and MA performances of GE-based magnetic hybrids arouse great attention in related fields. In this review, we summarize the recently progress in MA performance of GE-based magnetic hybrids. Typical absorption process and corresponding mechanism are firstly introduced, for guiding the design of GE-based magnetic MAMs. Then, the magnetic components, synthesis methods, structural features and regulation strategies of these GE-related magnetic materials are reviewed, and their influences on MA performances have also been discussed. Challenges, and prospects of the GE-based magnetic MAMs are suggested. This review provides a brief but systematic introduction to GE-based magnetic MAMs, which may pave the way for the design of MAMs with highly efficient MA performances.

Liquid metal assisted regulation of macro-/micro-structures and mechanical properties of nanoporous copper

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.