Nowadays,the rapid development of the social economy inevitably leads to global energy and environmental crisis.For this reason,more and more scholars focus on the development of photocatalysis and/or electrocatalysis...Nowadays,the rapid development of the social economy inevitably leads to global energy and environmental crisis.For this reason,more and more scholars focus on the development of photocatalysis and/or electrocatalysis technology for the advantage in the sustainable production of high-value-added products,and the high efficiency in pollutants remediation.Although there is plenty of outstanding research has been put forward continuously,most of them focuses on catalysis performance and reaction mechanisms in laboratory conditions.Realizing industrial application of photo/electrocatalytic processes is still a challenge that needs to be overcome by social demand.In this regard,this review comprehensively summarized several explorations in thefield of photo/electrocatalytic reduction towards potential industrial applications in recent years.Special attention is paid to the successful attempts and the current status of photo/electrocatalytic water splitting,carbon dioxide conversion,resource utilization from waste,etc.,by using advanced reactors.The key problems and challenges of photo/electrocatalysis in future industrial practice are also discussed,and the possible development directions are also pointed out from the industry view.展开更多
Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key hal...Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.展开更多
Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked pol...Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.展开更多
Clean catalytic oxidation has a broad prospect in the modern chemical engineering and energy chemistry fields.However,unexpected over-oxidation and disruptive degradation are frequently induced by excessive reactive o...Clean catalytic oxidation has a broad prospect in the modern chemical engineering and energy chemistry fields.However,unexpected over-oxidation and disruptive degradation are frequently induced by excessive reactive oxygen species(ROS).Herein,we reported a new ROS-free approach to effectively drive O_(2) to be activated into highly reactive surface peroxo species through enzyme-mimicking mechanism.Benefiting from the dual-metal synergy effect between Cu and Co active sites,ROS(H_(2)O_(2) and OH•)is generated in situ while further scavenged completely into surface peroxo species,which gives rise to very high selectivity and extremely high carbon balance.For example,the CuCo/N-C catalyst affords>99.8%conversion and 94.5%selectivity to 2,5-furanedicarboxylic acid at 25℃ for 6 h in the aerobic oxidation of biomass platform 5-hydroxymethylfurfural.Moreover,it achieved exceptional performance in the oxidation of a variety of hydroxyl compounds to organic acids with high yields(89.9%–99.5%)at a mild temperature(25–40℃).This exploration introduces an innovative clue for emulating enzyme catalysts,thereby enriching our comprehension and advancement of biologically inspired catalytic oxidations.展开更多
The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance.Despite extensive research on the identification and formation mechanism of ex...The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance.Despite extensive research on the identification and formation mechanism of extra-framework aluminum(EFAl),its impact on catalytic performance requires further investigation.Herein,mordenite(MOR)zeolites with comparable acid density within the 8MR and 12MR channels but different EFAl contents were prepared,and their catalytic roles were examined in syngas conversion.Intelligent gravimetric analysis,model experiment of ethylene conversion and thermogravimetric analysis demonstrate that the existence of EFAl species can inhibit the secondary conversion of ethylene to long chain hydrocarbons(i.e.,C_(5+))as well as the over-accumulation of carbonaceous species.However,excessive EFAl species lead to rapid deactivation due to restricted space and thus severe diffusion limitation.MOR zeolite with a moderate amount of EFAl species achieves a superior ethylene selectivity and exhibits an enhanced stability in syngas conversion when combined with ZnAlOx oxide.The insights gained in this work provide important guidance for the design of more efficient zeolite-based catalysts.展开更多
Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive st...Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.展开更多
The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly unders...The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.展开更多
Li-CO_(2)batteries are highly anticipated as promising candidates for advanced electrochemical energy storage systems owing to their high theoretical specific energy of 1876 Wh kg^(-1),based on the discharge products ...Li-CO_(2)batteries are highly anticipated as promising candidates for advanced electrochemical energy storage systems owing to their high theoretical specific energy of 1876 Wh kg^(-1),based on the discharge products of Li_(2)CO_(3)and C,their environmentally benign CO_(2)utilization [1].Since CO_(2)is the main component of the atmosphere on Mars,Li-CO_(2)batteries can serve as an excellent power source for Mars exploration missions.However,several key issues remain unresolved,such as the slow kinetics of CO_(2)reduction reaction(CRR) and CO_(2)evolution reaction(CER),the severe side reaction between Li with CO_(2),and the risk of the electrolyte combustion due to thermal runaway,all of which hinder the practical application of Li-CO_(2)batteries.展开更多
Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and ca...Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.展开更多
Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% ...Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% CO2 conversion with 99.5% CH4 selectivity at 350℃, which was much better than its impregnated counterpart. Characterizations by means of CO2 microcalorimetry and 27 Al NMR indicated that large amount of strong basic sites existed on Ni-Al2O3-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO2 and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction. Keywords展开更多
Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenge...Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy‐related electrocatalytic reactions.Compared with conventional wet‐chemical,solid‐state and vapor deposition synthesis,electrochemical synthesis is a simple,fast,cost‐effective and precisely controllable method for the preparation of highly efficient catalytic materials.In this review,we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms,spherical and shaped nanoparticles,nanosheets,nanowires,core‐shell nanostructures,layered nanomaterials,dendritic nanostructures,hierarchically porous nanostructures as well as composite nanostructures.Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed.Structure‐performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples.We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods,and we propose some research challenges and future opportunities in this field.展开更多
The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and pre...The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and preferential oxidation of CO in H2.The last six years have witnessed tremendous progress in the field of single‐atom catalysis.Here we introduce the major achievements on this topic in2015and2016.Some particular aspects of single‐atom catalysis are discussed in depth,including new approaches in single‐atom catalyst(SAC)synthesis,stable gold SACs for various reactions,the high selectivity of Pt and Pd SACs in hydrogenation,and the superior performance of non‐noble metal SACs in electrochemistry.These accomplishments will encourage more efforts by researchers to achieve the controllable fabrication of SACs and explore their potential applications.展开更多
A versatile wet chemistry method is developed for filling of subnanometer sized metal particles in carbon nanotubes with a diameter smaller than 1.5 nm. As an example, we showed that a confined bi-component Pd-V catal...A versatile wet chemistry method is developed for filling of subnanometer sized metal particles in carbon nanotubes with a diameter smaller than 1.5 nm. As an example, we showed that a confined bi-component Pd-V catalyst exhibit a higher benzene hydroxylation activity compared with that within multi-walled carbon nanotubes.展开更多
The development of catalytic materials for the recycling CO_(2) through a myriad of available processes is an attractive field,especially given the current climate change.While there is increasing publication in this ...The development of catalytic materials for the recycling CO_(2) through a myriad of available processes is an attractive field,especially given the current climate change.While there is increasing publication in this field,the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology,with the most simplistic method of enhancement being the addition of more metals to an already complex composition.Encapsulated catalysts,especially yolk@shell catalysts with hollow voids,offer answers to the most prominent issues faced by this field,coking and sintering,and further potential for more advanced phenomena,for example,the confinement effect,to promote selectivity or offer greater protection against coking and sintering.This work serves to demonstrate the current position of catalyst development in the fields of thermal CO_(2) reforming and hydrogenation,summarizing the most recent work available and most common metals used for these reactions,and how yolk@shell catalysts can offer superior performance and survivability in thermal CO_(2) reforming and hydrogenation to the more traditional structure.Furthermore,this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure.Moreover,this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.展开更多
The size-dependent nanocatalysis has been well studied in the past three decades,while little concern is paid to the shape of the nanoparticles,which can greatly modify the reaction performance by selectively exposing...The size-dependent nanocatalysis has been well studied in the past three decades,while little concern is paid to the shape of the nanoparticles,which can greatly modify the reaction performance by selectively exposing specific crystal facets.This article highlights the recent progress on the morphology-dependent nanocatalysis published in Chinese Journal of Catalysis of the year 2010.This strategy should be workable in designing and preparing efficient nanocatalysts with tunable size and shape.展开更多
The photocatalytic hydrogen evolution and electrochemical behaviors of Kiggen-type XW12O40^n- （X=P, Ge and Si） are investigated. It is found that the two-electron reduced species are active for H^＋ reduction and th...The photocatalytic hydrogen evolution and electrochemical behaviors of Kiggen-type XW12O40^n- （X=P, Ge and Si） are investigated. It is found that the two-electron reduced species are active for H^＋ reduction and the more negative the potential of XW12O40^（n＋2）-/（n＋1）- is, the higher the activity for hydrogen evolution is.展开更多
Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electr...Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.展开更多
Cytochrome P450 enzymes catalyze diverse oxidative transformations at the expense of reduced nicotinamide adenine dinucleotide phosphate(NADPH),however,their applications remain limited largely because NADPH is cost-p...Cytochrome P450 enzymes catalyze diverse oxidative transformations at the expense of reduced nicotinamide adenine dinucleotide phosphate(NADPH),however,their applications remain limited largely because NADPH is cost-prohibitive for biocatalysis at scale yet tightly regulated in host cells.A highly challenging task for P450 catalysis has been to develop an alternative and biocompatible electrondonating system.Here we engineered P450 BM3 to favor reduced nicotinamide cytosine dinucleotide(NCDH)and created non-natural cofactor-dependent P450 catalysis.Two outstanding mutants were identified with over 640-fold NCDH preference improvement and good catalytic efficiencies of over15,000 M^(-1)s^(-1)for the oxidation of the fatty acid probe 12-(para-nitrophenoxy)-dodecanoate.Molecular docking analysis indicated that these mutants bear a compacted cofactor entrance.Upon fusing with an NCD-dependent formate dehydrogenase,fused proteins functioned as NCDH-specific P450catalysts by using formate as the electron donor.Importantly,these mutants and fusions catalyzed NCDH-dependent hydroxylation of fatty acids with similar chain length preference to those by natural P450 BM3 in the presence of NADPH and also similar regioselectivity for subterminal hydroxylation of lauric acid.As P450 BM3 and its variants are catalytically powerful to take diverse substrates and convey different reaction paths,our results offer an exciting opportunity to devise advanced cell factories that convey oxidative biocatalysis with an orthogonal reducing power supply system.展开更多
Electrochemical capacitors(ECs)with unique merits of fast charge/discharge rate and long cyclability are one of the representative electrochemical energy storage systems,possessing wide applications in power electroni...Electrochemical capacitors(ECs)with unique merits of fast charge/discharge rate and long cyclability are one of the representative electrochemical energy storage systems,possessing wide applications in power electronics and automotive transportation,etc.[1,2].Furthermore.展开更多
基金supported by the National Natural Science Foundation of China(22278030,22090032,22090030,22288102,22242019)the Fundamental Research Funds for the Central Universities(buctrc202119,2312018RC07)+1 种基金Major Program of Qingyuan Innovation Laboratory(Grant No.001220005)the Experiments for Space Exploration Program and the Qian Xuesen Laboratory,China Academy of Space Technology。
文摘Nowadays,the rapid development of the social economy inevitably leads to global energy and environmental crisis.For this reason,more and more scholars focus on the development of photocatalysis and/or electrocatalysis technology for the advantage in the sustainable production of high-value-added products,and the high efficiency in pollutants remediation.Although there is plenty of outstanding research has been put forward continuously,most of them focuses on catalysis performance and reaction mechanisms in laboratory conditions.Realizing industrial application of photo/electrocatalytic processes is still a challenge that needs to be overcome by social demand.In this regard,this review comprehensively summarized several explorations in thefield of photo/electrocatalytic reduction towards potential industrial applications in recent years.Special attention is paid to the successful attempts and the current status of photo/electrocatalytic water splitting,carbon dioxide conversion,resource utilization from waste,etc.,by using advanced reactors.The key problems and challenges of photo/electrocatalysis in future industrial practice are also discussed,and the possible development directions are also pointed out from the industry view.
基金support from National Natural Science Foundation of China(Grant Nos.22125903,22209174)the National Key R&D Program of China(Grants 2022YFA1504100)+2 种基金Dalian Innovation Support Plan for High Level Talents(2019RT09)Dalian National Laboratory For Clean Energy(DNL),CAS,DNL Cooperation Fund,CAS(DNL202016,DNL202019)DICP(DICP I2020032).
文摘Electricity-driven water splitting to produce hydrogen is one of the most efficient ways to alleviate energy crisis and environmental pollution problems,in which the anodic oxygen evolution reaction(OER)is the key half-reaction of performance-limiting in water splitting.Given the complicated reaction process and surface reconstruction of the involved catalysts under actual working conditions,unraveling the real active sites,probing multiple reaction intermediates and clarifying catalytic pathways through in-situ characterization techniques and theoretical calculations are essential.In this review,we summarize the recent advancements in understanding the catalytic process,unlocking the water oxidation active phase and elucidating catalytic mechanism of water oxidation by various in-situ characterization techniques.Firstly,we introduce conventionally proposed traditional catalytic mechanisms and novel evolutionary mechanisms of OER,and highlight the significance of optimal catalytic pathways and intrinsic stability.Next,we provide a comprehensive overview of the fundamental working principles,different detection modes,applicable scenarios,and limitations associated with the in-situ characterization techniques.Further,we exemplified the in-situ studies and discussed phase transition detection,visualization of speciation evolution,electronic structure tracking,observation of reaction active intermediates,and monitoring of catalytic products,as well as establishing catalytic structure-activity relationships and catalytic mechanism.Finally,the key challenges and future perspectives for demystifying the water oxidation process are briefly proposed.
基金financially supported by the National Natural Science Foundation of China(Grant No.22325405,22321002,22279153)Liaoning Revitalization Talents Program(XLYC1807207,XLYC2203134)DICP I202104。
文摘Solid polymer electrolytes(SPEs)have become increasingly important in advanced lithium-ion batteries(LIBs)due to their improved safety and mechanical properties compared to organic liquid electrolytes.Cross-linked polymers have the potential to further improve the mechanical property without trading off Li-ion conductivity.In this study,focusing on a recently developed cross-linked SPE,i.e.,the one based on poly(vinylene carbonate)-poly(ethylene oxide)cross-linked network(PVCN),we used solid-state nuclear magnetic resonance(NMR)techniques to investigate the fundamental interaction between the chain segments and Li ions,as well as the lithium-ion motion.By utilizing homonuclear/heteronuclear correlation,CP(cross-polarization)kinetics,and spin-lattice relaxation experiments,etc.,we revealed the structural characteristics and their relations to lithium-ion mobilities.It is found that the network formation prevents poly(ethylene oxide)chains from crystallization,which could create sufficient space for segmental tumbling and Li-ion co nductio n.As such,the mechanical property is greatly improved with even higher Li-ion mobilities compared to the poly(vinylene carbonate)or poly(ethylene oxide)based SPE analogues.
文摘Clean catalytic oxidation has a broad prospect in the modern chemical engineering and energy chemistry fields.However,unexpected over-oxidation and disruptive degradation are frequently induced by excessive reactive oxygen species(ROS).Herein,we reported a new ROS-free approach to effectively drive O_(2) to be activated into highly reactive surface peroxo species through enzyme-mimicking mechanism.Benefiting from the dual-metal synergy effect between Cu and Co active sites,ROS(H_(2)O_(2) and OH•)is generated in situ while further scavenged completely into surface peroxo species,which gives rise to very high selectivity and extremely high carbon balance.For example,the CuCo/N-C catalyst affords>99.8%conversion and 94.5%selectivity to 2,5-furanedicarboxylic acid at 25℃ for 6 h in the aerobic oxidation of biomass platform 5-hydroxymethylfurfural.Moreover,it achieved exceptional performance in the oxidation of a variety of hydroxyl compounds to organic acids with high yields(89.9%–99.5%)at a mild temperature(25–40℃).This exploration introduces an innovative clue for emulating enzyme catalysts,thereby enriching our comprehension and advancement of biologically inspired catalytic oxidations.
文摘The location of aluminum within the framework or extra-framework of zeolites is a critical factor in determining its catalytic performance.Despite extensive research on the identification and formation mechanism of extra-framework aluminum(EFAl),its impact on catalytic performance requires further investigation.Herein,mordenite(MOR)zeolites with comparable acid density within the 8MR and 12MR channels but different EFAl contents were prepared,and their catalytic roles were examined in syngas conversion.Intelligent gravimetric analysis,model experiment of ethylene conversion and thermogravimetric analysis demonstrate that the existence of EFAl species can inhibit the secondary conversion of ethylene to long chain hydrocarbons(i.e.,C_(5+))as well as the over-accumulation of carbonaceous species.However,excessive EFAl species lead to rapid deactivation due to restricted space and thus severe diffusion limitation.MOR zeolite with a moderate amount of EFAl species achieves a superior ethylene selectivity and exhibits an enhanced stability in syngas conversion when combined with ZnAlOx oxide.The insights gained in this work provide important guidance for the design of more efficient zeolite-based catalysts.
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
基金Joint Project of Dalian University of Technology-Dalian Institute of Chemical Physics (HX20230236)。
文摘Zeolite nanosheets with a short b-axis thickness are highly desirable in lots of catalytic reactions due to their reduced diffusion resistance. Nevertheless, conventional synthesis methods usually require expensive structure-directing agents(SDAs), pricey raw materials, and eco-unfriendly fluorine-containing additives. Here, we contributed a cost-effective and fluoride-free synthesis method for synthesizing high-quality MFI zeolite nanosheets through a Silicalite-1(Sil-1) seed suspension and urea cooperative strategy, only with inexpensive colloidal silica as the Si source. Our approach was effective for synthesizing both Sil-1 and aluminum-containing ZSM-5 nanosheets. By optimizing key synthesis parameters,including seed aging time, seed quantity, and urea concentration, we achieved precise control over the crystal face aspect ratio and b-axis thickness. We also revealed a non-classical oriented nanosheet growth mechanism, where Sil-1 seeds induced the formation of quasi-ordered precursor particles, and the(010)crystal planes of these particles facilitated urea adsorption, thereby promoting c-axis-oriented growth.The obtained ZSM-5 nanosheets exhibited exceptional catalytic performance in the benzene alkylation with ethanol, maintaining stability for over 500 h, which is 5 times longer than traditional ZSM-5 catalysts. Furthermore, large-scale production of ZSM-5 nanosheets was successfully carried out in a 3 L highpressure autoclave, yielding samples consistent with those from laboratory-scale synthesis. This work marks a significant step forward in the sustainable and efficient production of MFI nanosheets using inexpensive and environmentally friendly raw materials, offering the broad applicability in catalysis.
基金financially National Key R&D Program of China(No.2022YFA1504800)National Natural Science Foundation of China(Grant No.22325405,22372160,22321002)+1 种基金Liaoning Revitalization Talents Program(XLYC1807207)DICP I202104。
文摘The Zn-Al spinel oxide stands out as one of the most active catalysts for high-temperature methanol synthesis from CO_(2)hydrogenation.However,the structure–activity relationship of the reaction remains poorly understood due to challenges in atomic-level structural characterizations and analysis of reaction intermediates.In this study,we prepared two Zn-Al spinel oxide catalysts via coprecipitation(ZnAl-C)and hydrothermal(ZnAl-H)methods,and conducted a comparative investigation in the CO_(2)hydrogenation reaction.Surprisingly,under similar conditions,ZnAl-C exhibited significantly higher selectivity towards methanol and DME compared to ZnAl-H.Comprehensive characterizations using X-ray diffraction(XRD),Raman spectroscopy and electron paramagnetic resonance(EPR)unveiled that ZnAl-C catalyst had abundant ZnO species on its surface,and the interaction between the ZnO species and its ZnAl spinel oxide matrix led to the formation of oxygen vacancies,which are crucial for CO_(2)adsorption and activation.Additionally,state-of-the-art solid-state nuclear magnetic resonance(NMR)techniques,including ex-situ and in-situ NMR analyses,confirmed that the surface ZnO facilitates the formation of unique highly reactive interfacial formate species,which was readily hydrogenated to methanol and DME.These insights elucidate the promotion effects of ZnO on the ZnAl spinel oxide in regulating active sites and reactive intermediates for CO_(2)-to-methanol hydrogenation reaction,which is further evidenced by the significant enhancement in methanol and DME selectivity observed upon loading ZnO onto the ZnAl-H catalyst.These molecular-level mechanism understandings reinforce the idea of optimizing the ZnO-ZnAl interface through tailored synthesis methods to achieve activity-selectivity balance.
基金supported by the National Key R&D Program of China (2022YFA1504100)the National Natural Science Foundation of China (22125903 and 22439003)+1 种基金the Exploratory Research Project of Yanchang Petroleum International Limited and DICP (ychw-2022ky-01)the Energy Revolution S&T Program of Yulin Innovation Institute of Clean Energy (E412010508)。
文摘Li-CO_(2)batteries are highly anticipated as promising candidates for advanced electrochemical energy storage systems owing to their high theoretical specific energy of 1876 Wh kg^(-1),based on the discharge products of Li_(2)CO_(3)and C,their environmentally benign CO_(2)utilization [1].Since CO_(2)is the main component of the atmosphere on Mars,Li-CO_(2)batteries can serve as an excellent power source for Mars exploration missions.However,several key issues remain unresolved,such as the slow kinetics of CO_(2)reduction reaction(CRR) and CO_(2)evolution reaction(CER),the severe side reaction between Li with CO_(2),and the risk of the electrolyte combustion due to thermal runaway,all of which hinder the practical application of Li-CO_(2)batteries.
基金National Key R&D Program of China (2023YFA1508001 and 2023YFA1508002)National Natural Science Foundation of China (22272120 and U2202251)+1 种基金Hainan Province Science and Technology Special Fund(ZDYF2023SHFZ120)Research Foundation of Marine Science and Technology Collaborative Innovation Center of Hainan University (XTCX2022HYB01)。
文摘Methane, an abundant one-carbon(C_(1)) resource, is extensively used in the industrial production of vital fuels and value-added chemicals. However, current industrial methane conversion technologies are energy-and carbon-intensive, mainly due to the high activation energy required to break the inert C–H bond, low selectivity, and problematic side reactions, including CO_(2)emissions and coke deposition. Electrochemical conversion of methane(ECM) using intermittent renewable energy offers an attractive solution, due to its modular reactor design and operational flexibility across a broad spectrum of temperatures and pressures. This review emphasizes conversion pathways of methane in various reaction systems, highlighting the significance and advantages of ECM in facilitating a sustainable artificial carbon cycle. This work provides a comprehensive overview of conventional methane activation mechanisms and delineates the complete pathways of methane conversion in electrolysis contexts. Based on surface/interface chemistry, this work systematically analyzes proposed reaction pathways and corresponding strategies to enhance ECM efficiency towards various target products, including syngas, hydrocarbons, oxygenates, and advanced carbon materials. The discussion also encompasses opportunities and challenges for the ECM process, including insights into ECM pathways, rational electrocatalyst design, establishment of benchmarking protocols, electrolyte engineering, enhancement of CH4conversion rates, and minimization of CO_(2)emission.
基金supported by the National Natural Science Foundation of China(21103173)
文摘Ni-Al hydrotalcite derived catalyst （Ni-Al2O3-HT） exhibited a narrow Ni particle-size distribution with an average particle size of 4.0 nm. Methanation of CO2 over this catalyst initiated at 225℃ and reached 82.5% CO2 conversion with 99.5% CH4 selectivity at 350℃, which was much better than its impregnated counterpart. Characterizations by means of CO2 microcalorimetry and 27 Al NMR indicated that large amount of strong basic sites existed on Ni-Al2O3-HT, originated from the formation of Ni-O-Al structure. The existence of strong basic sites facilitated the activation of CO2 and consequently promoted the activity. The combination of highly dispersed Ni with strong basic support led to its unique and high efficiency for this reaction. Keywords
文摘Electrocatalysis is a process dealing with electrochemical reactions in the interconversion of chemical energy and electrical energy.Precise synthesis of catalytically active nanostructures is one of the key challenges that hinder the practical application of many important energy‐related electrocatalytic reactions.Compared with conventional wet‐chemical,solid‐state and vapor deposition synthesis,electrochemical synthesis is a simple,fast,cost‐effective and precisely controllable method for the preparation of highly efficient catalytic materials.In this review,we summarize recent progress in the electrochemical synthesis of catalytic materials such as single atoms,spherical and shaped nanoparticles,nanosheets,nanowires,core‐shell nanostructures,layered nanomaterials,dendritic nanostructures,hierarchically porous nanostructures as well as composite nanostructures.Fundamental aspects of electrochemical synthesis and several main electrochemical synthesis methods are discussed.Structure‐performance correlations between electrochemically synthesized catalysts and their unique electrocatalytic properties are exemplified using selected examples.We offer the reader with a basic guide to the synthesis of highly efficient catalysts using electrochemical methods,and we propose some research challenges and future opportunities in this field.
基金supported by the National Natural Science Foundation of China(21606222,21303184,21573232)China Postdoctoral Science Foundation(2016M601350)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(XDB17020100)National Key Projects for Fundamental Research and Development of China(2016YFA0202801)Department of Science and Technology of Liaoning Province(2015020086-101)~~
文摘The idea that single metal atoms dispersed on a solid support can act as an efficient heterogeneous catalyst was raised in2011when single Pt atoms on an FeOx surface were reported to be active for CO oxidation and preferential oxidation of CO in H2.The last six years have witnessed tremendous progress in the field of single‐atom catalysis.Here we introduce the major achievements on this topic in2015and2016.Some particular aspects of single‐atom catalysis are discussed in depth,including new approaches in single‐atom catalyst(SAC)synthesis,stable gold SACs for various reactions,the high selectivity of Pt and Pd SACs in hydrogenation,and the superior performance of non‐noble metal SACs in electrochemistry.These accomplishments will encourage more efforts by researchers to achieve the controllable fabrication of SACs and explore their potential applications.
基金supported by the National Natural Science Foundation of China (Grant No 21173215, 21033009 and 11079005)
文摘A versatile wet chemistry method is developed for filling of subnanometer sized metal particles in carbon nanotubes with a diameter smaller than 1.5 nm. As an example, we showed that a confined bi-component Pd-V catalyst exhibit a higher benzene hydroxylation activity compared with that within multi-walled carbon nanotubes.
基金Financial support was provided by the Chinese Academy of Sciences–The World Academy of Sciences(CAS-TWAS)president fellowship。
文摘The development of catalytic materials for the recycling CO_(2) through a myriad of available processes is an attractive field,especially given the current climate change.While there is increasing publication in this field,the reported catalysts rarely deviate from the traditionally supported metal nanoparticle morphology,with the most simplistic method of enhancement being the addition of more metals to an already complex composition.Encapsulated catalysts,especially yolk@shell catalysts with hollow voids,offer answers to the most prominent issues faced by this field,coking and sintering,and further potential for more advanced phenomena,for example,the confinement effect,to promote selectivity or offer greater protection against coking and sintering.This work serves to demonstrate the current position of catalyst development in the fields of thermal CO_(2) reforming and hydrogenation,summarizing the most recent work available and most common metals used for these reactions,and how yolk@shell catalysts can offer superior performance and survivability in thermal CO_(2) reforming and hydrogenation to the more traditional structure.Furthermore,this work will briefly demonstrate the bespoke nature and highly variable yolk@shell structure.Moreover,this review aims to illuminate the spatial confinement effect and how it enhances yolk@shell structured nanoreactors is presented.
文摘The size-dependent nanocatalysis has been well studied in the past three decades,while little concern is paid to the shape of the nanoparticles,which can greatly modify the reaction performance by selectively exposing specific crystal facets.This article highlights the recent progress on the morphology-dependent nanocatalysis published in Chinese Journal of Catalysis of the year 2010.This strategy should be workable in designing and preparing efficient nanocatalysts with tunable size and shape.
基金This work was financially supported by the National Natural Science Foundation of China （No.20273070）the National-Key Basic Research and Development Program （No. 2003CB214500）+1 种基金The authors also gratefully acknowledge the Liaoning-Provincial Science and Technology Commission （No. 200310592003）Dalian Municipal Science and Technology Commission for financial support.
文摘The photocatalytic hydrogen evolution and electrochemical behaviors of Kiggen-type XW12O40^n- （X=P, Ge and Si） are investigated. It is found that the two-electron reduced species are active for H^＋ reduction and the more negative the potential of XW12O40^（n＋2）-/（n＋1）- is, the higher the activity for hydrogen evolution is.
基金financially supported by the National Key R&D Program of China under contact No.2017YFA0204804the National Natural Science Foundation of China under contact Nos.21761142018,21473189 and 22088102 for supporting Fundamental Research Center of Artificial Photosynthesis(FRe CAP)。
文摘Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.
基金supported by the National Key R&D Program of China(2019YFA0904900)the National Natural Science Foundation of China(21877112,21837002,21721004)。
文摘Cytochrome P450 enzymes catalyze diverse oxidative transformations at the expense of reduced nicotinamide adenine dinucleotide phosphate(NADPH),however,their applications remain limited largely because NADPH is cost-prohibitive for biocatalysis at scale yet tightly regulated in host cells.A highly challenging task for P450 catalysis has been to develop an alternative and biocompatible electrondonating system.Here we engineered P450 BM3 to favor reduced nicotinamide cytosine dinucleotide(NCDH)and created non-natural cofactor-dependent P450 catalysis.Two outstanding mutants were identified with over 640-fold NCDH preference improvement and good catalytic efficiencies of over15,000 M^(-1)s^(-1)for the oxidation of the fatty acid probe 12-(para-nitrophenoxy)-dodecanoate.Molecular docking analysis indicated that these mutants bear a compacted cofactor entrance.Upon fusing with an NCD-dependent formate dehydrogenase,fused proteins functioned as NCDH-specific P450catalysts by using formate as the electron donor.Importantly,these mutants and fusions catalyzed NCDH-dependent hydroxylation of fatty acids with similar chain length preference to those by natural P450 BM3 in the presence of NADPH and also similar regioselectivity for subterminal hydroxylation of lauric acid.As P450 BM3 and its variants are catalytically powerful to take diverse substrates and convey different reaction paths,our results offer an exciting opportunity to devise advanced cell factories that convey oxidative biocatalysis with an orthogonal reducing power supply system.
基金financially supported by the National Natural Science Foundation of China(22125903,51872283,22005298)。
文摘Electrochemical capacitors(ECs)with unique merits of fast charge/discharge rate and long cyclability are one of the representative electrochemical energy storage systems,possessing wide applications in power electronics and automotive transportation,etc.[1,2].Furthermore.
