A review on the structure-performance relationship of the catalysts during propane dehydrogenation reaction

Dehydrogenation of propane(PDH)technology is one of the most promising on-purpose technologies to solve supply-demand unbalance of propylene.The industrial catalysts for PDH,such as Pt-and Cr-based catalysts,still have their own limitation in expensive price and security issues.Thus,a deep understanding into the structure-performance relationship of the catalysts during PDH reaction is necessary to achieve innovation in advanced high-efficient catalysts.In this review,we focused on discussion of structure-performance relationship of catalysts in PDH.Based on analysis of reaction mechanism and nature of active sites,we detailed interaction mechanism between structure of active sites and catalytic performance in metal catalysts and oxide catalysts.The relationship between coke deposition,co-feeding gas,catalytic activity and nanostructure of the catalysts are also highlighted.With these discussions on the relationship between structure and performances,we try to provide the insights into microstructure of active sites in PDH and the rational guidance for future design and development of PDH catalysts.

Cobalt-embedded few-layered carbon nanosheets toward enhanced hydrogen evolution:Rational design and insight into structure-performance correlation

Over the past decades, the energy and concomitant environment issues, such as energy shortage, air pollution and global warming, have been becoming increasingly striking world-wide challenges [1,2]. Such a dilemma in turn appeals to the development and employment of clean and renewable energy.

Lean methane combustion over zeolite-supported Pd catalysts:Structure-performance relationship and deactivation mechanism

Zeolites are a promising support for Pd catalysts in leanmethane(CH_(4))combustion.Herein,three types of zeolites(H-MOR,H-ZSM-5 and H-Y)were selected to estimate their structural effects and deactivation mechanisms in CH_(4)combustion.We show that variations in zeolite structure and surface acidity led to distinct changes in Pd states.Pd/H-MOR with external high-dispersing Pd nanoparticles exhibited the best apparent activity,with activation energy(Ea)at 73 kJ/mol,while Pd/H-ZSM-5 displayed the highest turnover frequency(TOF)at 19.6×10^(−3)sec^(−1),presumably owing to its large particles with more step sites providing active sites in one particle for CH_(4)activation.Pd/H-Y with dispersed PdO within pore channels and/or Pd2+ions on ion-exchange sites yielded the lowest apparent activity and TOF.Furthermore,Pd/H-MOR and Pd/H-ZSM-5 were both stable under a dry condition,but introducing 3 vol.%H_(2)O caused the CH_(4)conversion rate on Pd/H-MOR drop from 100%to 63%and that on Pd/H-ZSM-5 decreased remarkably from 82%to 36%.The former was shown to originate fromzeolite structural dealumination,and the latter principally owed to Pd aggregation and the loss of active PdO.

Effect of Sodium on the Structure-Performance Relationship of Co/SiO2 for Fischer-Tropsch Synthesis

A series of Co/SiO2 catalysts with different sodium （Na）loadings （0, 0.1, 0.2, 0.5 and I wt%） were prepared and evaluated for Fischer-Tropsch reaction to study the effect of Na on the catalyst structure and catalytic performance. The addition of Na was found to decrease the catalytic activity and hydrocarbon selectivity, but increase CO2 selec- tivity due to the enhanced WGS activity. The addition of Na also resulted in higher selectivity to oxygenates （alco- hols and aldehydes） and O/P ratio as well as the shift of hydrocarbons to lower carbon numbers. Structure charac- terization revealed a decrease in the surface area and particles size for the calcined samples with the addition of Na. CozC was formed during the reaction process for the Na-promoted catalysts. As a result, a new Co/Co2C bifunc- tional active sites were generated for oxygenates formation leading to increasing oxygenates selectivity. In addition, the Co2C nanoparticles alone may also act as dual active sites for oxygenate formation at high reaction pressure over the promoted catalysts with high Na loading.

In situ characterizations of advanced electrode materials for sodium-ion batteries toward high electrochemical performances

Energy storage is an ever-growing global concern due to increased energy needs and resource exhaustion.Sodium-ion batteries(SIBs)have called increasing attention and achieved substantial progress in recent years owing to the abundance and even distribution of Na resources in the crust,and the predicted low cost of the technique.Nevertheless,SIBs still face challenges like lower energy density and inferior cycling stability compared to mature lithium-ion batteries(LIBs).Enhancing the electrochemical performance of SIBs requires an in-deep and comprehensive understanding of the improvement strategies and the underlying reaction mechanism elucidated by in situ techniques.In this review,commonly applied in situ techniques,for instance,transmission electron microscopy(TEM),Raman spectroscopy,X-ray diffraction(XRD),and X-ray absorption near-edge structure(XANES),and their applications on the representative cathode and anode materials with selected samples are summarized.We discuss the merits and demerits of each type of material,strategies to enhance their electrochemical performance,and the applications of in situ characterizations of them during the de/sodiation process to reveal the underlying reaction mechanism for performance improvement.We aim to elucidate the composition/structure-per formance relationship to provide guidelines for rational design and preparation of electrode materials toward high electrochemical performance.

Structure-guided Capacitance Relationships in Oxidized Graphene Porous Materials Based Supercapacitors

Supercapacitors formed from porous carbon and graphene-oxide(GO)materials are usually dominated by either electric double-layer capacitance,pseudo-capacitance,or both.Due to these combined features,reduced GO materials have been shown to offer superior capacitance over typical nanoporous carbon materials;however,there is a significant variation in reported values,ranging between 25 and 350 F g^(−1).This undermines the structure(e.g.,oxygen functionality and/or surface area)-performance relationships for optimization of cost and scalable factors.This work demonstrates important structure-controlled charge storage relationships.For this,a series of exfoliated graphene(EG)derivatives are produced via thermal-shock exfoliation of GO precursors and following controlled graphitization of EG(GEG)generates materials with varied amounts of porosity,redox-active oxygen groups and graphitic components.Experimental results show significantly varied capacitance values between 30 and 250 F g^(−1)at 1.0 A g^(−1)in GEG structures;this suggests that for a given specific surface area the redox-active and hydrophilic oxygen content can boost the capacitance to 250–300%higher compared to typical mesoporous carbon materials.GEGs with identical oxygen functionality show a surface area governed capacitance.This allows to establish direct structure-performance relationships between 1)redox-active oxygen functional concentration and capacitance and 2)surface area and capacitance.

Recent advances in electrospun electrode materials for sodium-ion batteries

Sodium-ion batteries(SIBs)have been considered as an ideal choice for the next generation large-scale energy storage applications owing to the rich sodium resources and the analogous working principle to that of lithium-ion batteries(LIBs).Nevertheless,the larger size and heavier mass of Na^(+)ion than those of Li^(+)ion often lead to sluggish reaction kinetics and inferior cycling life in SIBs compared to the LIB counterparts.The pursuit of promising electrode materials that can accommodate the rapid and stable Na-ion insertion/extraction is the key to promoting the development of SIBs toward a commercial prosperity.One-dimensional(1 D)nanomaterials demonstrate great prospects in boosting the rate and cycling performances because of their large active surface areas,high endurance for deformation stress,short ions diffusion channels,and oriented electrons transfer paths.Electrospinning,as a versatile synthetic technology,features the advantages of controllable preparation,easy operation,and mass production,has been widely applied to fabricate the 1 D nanostructured electrode materials for SIBs.In this review,we comprehensively summarize the recent advances in the sodium-storage cathode and anode materials prepared by electrospinning,discuss the effects of modulating the spinning parameters on the materials’micro/nano-structures,and elucidate the structure-performance correlations of the tailored electrodes.Finally,the future directions to harvest more breakthroughs in electrospun Na-storage materials are pointed out.

Fundamental aspects in CO_(2) electroreduction reaction and solutions from in situ vibrational spectroscopies

Using renewable energy to drive carbon dioxide reduction reaction(CO_(2)RR)electrochemically into chemicals with high energy density is an efficient way to achieve carbon neutrality,where the effective utilization of CO_(2) and the storage of renewable energy are realized.The reactivity and selectivity of CO_(2)RR depend on the structure and composition of the catalyst,applied potential,electrolyte,and pH of the solution.Besides,multiple electron and proton transfer steps are involved in CO_(2)RR,making the reaction pathways even more complicated.In pursuit of molecular-level insights into the CO_(2)RR processes,in situ vibrational methods including infrared,Raman and sum frequency generation spectroscopies have been deployed to monitor the dynamic evolution of catalyst structure,to identify reactive intermediates as well as to investigate the effect of local reaction environment on CO_(2)RR performance.This review summarizes key findings from recent electrochemical vibrational spectrosopic studies of CO_(2)RR in addressing the following issues:the CO_(2)RR mechanisms of different pathways,the role of surface-bound CO species,the compositional and structural effects of catalysts and electrolytes on CO_(2)RR activity and selectivity.Our perspectives on developing high sensitivity wide-frequency infrared spectroscopy,coupling different spectroelectrochemical methods and implementing operando vibrational spectroscopies to tackle the CO_(2)RR process in pilot reactors are offered at the end.

Effective synthesis of 5-amino-1-pentanol by reductive amination of biomass-derived 2-hydroxytetrahydropyran over supported Ni catalysts

A highly efficient and green process was developed for the synthesis of useful 5-amino-1-pentanol(5-AP)from biomass-derived dihydropyran by coupling the in situ generation of 5-hydroxypentanal(5-HP,via the ring-opening tautomerization of 2-hydroxytetrahydropyran(2-HTHP))and its reductive amination over supported Ni catalysts.The catalytic performances of the supported Ni catalysts on different oxides including SiO2,TiO2,ZrO2,γ-Al2 O3,and MgO as well as several commercial hydrogenation catalysts were investigated.The Ni/ZrO2 catalyst presented the highest 5-AP yield.The characterization results of the oxide-supported Ni catalysts showed that the Ni/ZrO2 catalyst possessed high reducibility and a high surface acid density,which lead to the enhanced activity and selectivity of the catalyst.The effect of reaction parameters on the catalytic performance of the Ni/ZrO2 catalyst was studied,and a high 5-AP yield of 90.8%was achieved in the reductive amination of 2-HTHP aqueous solution under mild conditions of 80℃and 2 MPa H2.The stability of the Ni/ZrO2 catalyst was studied using a continuous flow reactor,and only a slight decrease in the 5-AP yield was observed after a 90-h time-on-stream.Additionally,the reaction pathways for the reductive amination of 2-HTHP to synthesize 5-AP were proposed.

Interface-directed epitaxially growing nickle ensembles as efficient catalysts in dry reforming of methane

Supported nickel catalysts are promising candidates for dry reforming of methane, but agglomeration of Ni^(0) and coke deposition hinder the industrial applications. Herein, we report a novel interface-directed synthetic approach to construct distinct metal ensembles by carefully tuning the compositions of the carriers. A Zr-Mn-Zn ternary oxide-supported Ni catalyst, together with the respective binary oxide-supported analogues, was synthesized by adopting a sequential co-precipitation and wetness impregnation method. Combined characterization techniques identify distinct catalyst models, including (i) conventional NiO nanoparticles with different sizes on Zr-Mn and Zr-Zn, and (ii) epitaxially growing NiO ensembles of a few nanometers thickness at the periphery of ZnO_(x) particles. These catalysts exhibit divergent responses in the catalytic testing, with the ternary oxide system significantly outperforming the binary analogues. The strong electronic interactions between Mn-Ni increase Ni dispersion and the activity while the stability is strengthened upon Zn addition. Both high activity, high selectivity, and remarkable stability are attained upon co-adding Mn and Zn. The interfaces between Ni and Zr-Mn-Zn rather than the physical contacts of individual oxide-supported analogues through mechanical mixing are keys for the outstanding performance.

Restructuring of well-defined Pt-based electrode surfaces under mild electrochemical conditions

Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.

钌基单原子和团簇催化剂在电催化反应中的竞争和协同效应

单原子和团簇催化剂在电催化领域,尤其是可持续能源存储和转化领域的重要性,得到越来越多地认可.单原子催化剂具有低金属负载和高原子利用效率的优点,但由于其表面自由能常常使得单个原子不稳定而发生聚集.团簇催化剂则因为其高原子利用率以及多样的活性位点,能够克服单原子催化剂在中间体吸附和活化等方面的局限性.钌基催化剂在电催化中有着十分重要的应用前景.然而,准确设计钌基单原子和团簇催化剂的几何和电子结构,并揭示它们之间的结构-性质关系,仍然面临着巨大的挑战.因此,我们对钌基催化剂进行了分类和比较(同源/异源),重点总结了钌基单原子和团簇在电催化领域的竞争和协同效应.近年来,钌基催化剂在析氢反应(HER)方面取得了显著进展,因此着重介绍钌基催化剂在HER中的应用,并涵盖了其他电催化反应、双功能反应(HER/OER、HER/HOR)和电化学有机反应.此外,本文还探讨了钌基单原子和团簇在HER过程中的催化机理.最后,我们指出了在复杂钌基催化剂的工业应用开发策略中所面临的挑战和前景.

Multi-scale structure engineering of covalent organic framework for electrochemical charge storage

Covalent organic frameworks(COFs),which are constructed by linking organic building blocks via dynamic covalent bonds,are newly emerged and burgeoning crystalline porous copolymers with features including programmable topological architecture,pre-designable periodic skeleton,well-defined micro-/meso-pore,large specific surface area,and customizable electroactive functionality.Those benefits make COFs as promising candidates for advanced electrochemical energy storage.Especially,for now,structure engineering of COFs from multiscale aspects has been conducted to enable optimal overall electrochemical performance in terms of structure durability,electrical conductivity,redox activity,and charge storage.In this review,we give a fundamental and insightful study on the correlations between multi-scale structure engineering and eventual electrochemical properties of COFs,started with introducing their basic chemistries and charge storage principles.The careful discussion on the significant achievements in structure engineering of COFs from linkages,redox sites,polygon skeleton,crystal nanostructures,and composite microstructures,and further their effects on the electrochemical behavior of COFs are presented.Finally,the timely cutting-edge perspectives and in-depth insights into COFbased electrodematerials to rationally screen their electrochemical behaviors for addressing future challenges and implementing electrochemical energy storage applications are proposed.

∼2.5 nm pores in carbon-based cathode promise better zinc-iodine batteries

The relationship mechanism between the material pore structures and cathodic iodine chemistry plays a vital role in efficient Zn-I_(2) batteries,but is unclear,retarding further advances.This work innovatively indicates a great contribution of∼2.5nm pore structure of nanocarbons to efficient iodine adsorption,rapid I^(−)↔I_(2) conversion,and polyiodide inhibition,via scrupulously designing catalysts with controllable pore sizes systematically.The I_(2)-loading within the designed nitrogen-doped nanocarbons can reach up to as high as 60.8 wt%.The batteries based on the cathode deliver impressive performances with a large capacity of 178.8 mAh/g and long-term cycling stability more than 4000 h at 5.0 C.Notably,these is no polyiodide such as I_(3)−and I_(5)−detected during the charge-discharge processes from comprehensive electrochemical cyclic voltammetry,X-ray photoelectron spectroscopy,and Raman technique.This work provides a novel knowledge-guided concept for rational pore design,promising better Zn-I_(2) batteries,which is also hoped to benefit other advanced energy technologies,such as Li-S,Li-ion,and Al-I_(2) batteries.

Structural insights into lithium-deficient type Li-rich layered oxide for high-performance cathode

As one of the promising candidate cathode materials for the high-performance lithium-ion batteries,Li-rich layered oxides still suffer from a series of critical drawbacks,such as voltage decay,oxygen release,irrevers-ible migration of transition metal ions,etc.In this work,Li-deficient method has been confirmed as an effective approach to improve the overall electrochemical performances of Li-rich cathode.The optimized lithium-deficient Li-rich layered cathode exhibits splendid discharge capacity of~297 mAh/g at 0.1 C and prominent rate per-formance of-143 mAh/g at 5 C.Subsequently,neutron diffraction in combination with Raman spectroscopy is applied to explore and clarify the underlying mechanism for improved performances.It was found that the lithium-deficient induced nickel migration and oxygen vacancy play an significant role in improving electro-chemical performances,because migration of nickel into Li layer is able to expand the Li layer spacing and reduce the Li/Ni antisite,leading to facilitated diffusion of lithium ions.Moreover,the formation of oxygen vacancy is able to promote anionic redox processes and suppress the gas release,thus leading to higher capacity.The results present valuable structural insights into the influence of lithium deficiency and provide guidance for the devel-opment of Li-rich cathode materials.

Manipulation of the PdAu-PdAuO_(x)interface on Pd-Au bimetallic catalysts for the direct synthesis of hydrogen peroxide

Direct synthesis of H_(2)O_(2)from H_(2) and O_(2)via heterogeneous catalysis is an environmentally friendly and atomically economic alternative to the traditional anthraquinone oxidation(AO)process.Optimizing the electronic and geometric structures of the active metals to break the current limitations of hydrogenation rate and H_(2)O_(2)selectivity is a promising and challenging topic.In this study,a series of Pd-Au bimetallic catalysts supported on TiO_(2)with a metal loading of 3.0 wt%and a constant Pd/Au molar ratio(Pd:Au=2:1)were prepared.The catalysts were reduced in H_(2) at different temperatures(473,573 and 673 K),and their catalytic activity for the direct H_(2)O_(2)synthesis were evaluated at 283 K and 0.1MPa.H_(2) reduced Pd-Au catalysts exhibited superior performance in direct H_(2)O_(2)synthesis.The maximum H_(2)O_(2)selectivity of 87.7%and H_(2)O_(2)yield of 3116.4 mmol h^(−1) gPd^(−1) were achieved over the Pd_(2.0)Au_(1.0)-573 catalyst with a H_(2) conversion of 12.8%.The tailored local chemical environment caused by H_(2) reduction creates a balanced ratio of Pd0 and PdO_(x) sites,thus improving the selectivity towards H_(2)O_(2).This work developed an effective strategy for fabrication of highly active and stable Pd-based H_(2)O_(2)synthesis catalysts with high H_(2)O_(2)yield.

Understanding the structure–performance relationship of active sites at atomic scale

Metal-based atomically dispersed catalysts have attracted more attention because of their excellent catalytic performance and nearly 100%atom utilization.Therefore,it is very important to comprehensively and systematically understand the relationship between catalytic active sites and catalytic performance at atomic scale.Here,we discuss and summarize in detail the key and fundamental factors affecting the active site,and relate them to the catalytic performance.First,we describe the effectiveness of active site design by coordination effects.Then,the role of chemical bonds in the active sites in changing the reaction performance is discussed.In addition,for intermetallic compounds,we explore how the spacing of active atoms affects the catalytic behavior.Moreover,the importance of synergistic effect in catalyst design is further discussed.Finally,the key parameters affecting the catalytic performance at atomic scale are summarized,and the main challenges and development prospects of atomic catalysts in the future are put forward.

Emerging low-nuclearity supported metal catalysts with atomic level precision for efficient heterogeneous catalysis

Supported atomically dispersed metal catalysts(ADMCs)have received enormous attention due to their high atom utilization efficiency,mass activity and excellent selectivity.Single-atom site catalysts(SACs)with monometal-center as the quintessential ADMCs have been extensively studied in the catalysis-related fields.Beyond SACs,novel atomically dispersed metal catalysts(NADMCs)with flexible active sites featuring two or more catalytically centers including dual-atom and triple-atom catalysts have drawn ever-increasing attention recently.Owing to the presence of multiple neighboring active sites,NADMCs could exhibit much higher activity and selectivity compared with SACs,especially in those complicated reactions with multi-step intermediates.This review comprehensively outlines the recent exciting advances on the NADMCs with emphasis on the deeper understanding of the synergistic interactions among multiple metal atoms and underlying structure-performance relationships.It starts with the systematical introduction of principal synthetic approaches for NADMCs highlighting the key issues of each fabrication method including the atomically precise control in the design of metal nuclearity,and then the state-of-the-art characterizations for identifying and monitoring the atomic structure of NADMCs are explored.Thereafter,the recent development of NADMCs in energy-related applications is systematically discussed.Finally,we provide some new insights into the remaining challenges and opportunities for the development of NADMCs.

Recent advances in non-noble electrocatalysts for oxidative valorization of biomass derivatives

Electrocatalysis is deemed as a promising approach for sustainable energy conversion and chemical production.Although a variety of cathode reactions(e.g.,hydrogen evolution and CO_(2)/N_(2)reduction)produce valuable fuels and chemicals,the extensively studied oxygen evolution reaction(OER)at anode only generates O_(2),which is not a high-value product.Substituting the OER with thermodynamically more favorable biomass derivative oxidation reactions(BDORs)not only enables energy-saving electrocatalysis,but also provides value-added anode products.Recent achievements have demonstrated that non-noble electrocatalysts are promising for BDORs.Herein,we provide a comprehensive review on recent achievements in the field of electrochemical BDORs catalyzed by non-noble catalysts.We start by summarizing the electrocatalytic oxidation of different types of biomass-derived substrates,aiming to show the advantages of the electrocatalytic pathway and to introduce the state-of-the-art non-noble catalysts.The reaction mechanisms of non-noble-material-catalyzed BDORs are then summarized and classified into three types according to the acceptor of hydrogen species during the dehydrogenation of biomass derivatives.Subsequently,discussions are devoted to the strategies for promoting the performances of non-noble electrocatalysts.Finally,we propose our opinions regarding future trends and major challenges in this field.

Boosting oxygen reduction activity of spinel CoFe2O4 by strong interaction with hierarchical nitrogen-doped carbon nanocages

The unique hierarchical nitrogen-doped carbon nanocages(h NCNC) are used as a new support to homogeneously immobilize spinel Co Fe_2O_4 nanoparticles by a facile solvothermal method. The so-constructed hierarchical Co Fe_2O_4/h NCNC catalyst exhibits a high oxygen reduction activity with an onset potential of0.966 V and half-wave potential of 0.819 V versus reversible hydrogen electrode, far superior to the corresponding 0.846 and 0.742 V for its counterpart of Co Fe_2O_4/h CNC with undoped hierarchical carbon nanocages(h CNC) as the support, which locates at the top level for spinel-based catalysts to date.Consequently, the Co Fe_2O_4/h NCNC displays the superior performance to the Co Fe_2O_4/h CNC, when used as the cathode catalysts in the home-made Al-air batteries. X-ray photoelectron spectroscopy characterizations reveal the more charge transfer from Co Fe_2O_4 to h NCNC than to h CNC, indicating the stronger interaction between Co Fe_2O_4 and h NCNC due to the nitrogen participation. The enhanced interaction and hierarchical morphology favor the high dispersion and modification of electronic states for the active species as well as the mass transport during the oxygen reduction process, which plays a significant role in boosting the electrocatalytic performances. In addition, we noticed the high sensitivity of O 1 s spectrum to the particle size and chemical environment for spinel oxides, which is used as an indicator to understand the evolution of ORR activities for all the Co Fe_2O_4-related contrast catalysts. Accordingly,the well-defined structure-performance relationship is demonstrated by the combination of experimental characterizations with theoretical calculations. This study provides a promising strategy to develop efficient, inexpensive and durable oxygen reduction electrocatalysts by tuning the interaction between spinel metal oxides and the carbon-based supports.