With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,off...With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.展开更多
To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environment...To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environmental processing applications due to their exceptionally high surface areas,large pore sizes,and enough pore volumes.These properties might enhance the performance of materials concerning adsorption/catalysis capability,durability,and stability.In this review,we enumerate the ordered mesoporous materials as adsorbents/catalysts and their modifications in water pollution treatment from the past decade,including heavy metals(Hg^(2+),Pb^(2+),Cd^(2+),Cr^(6+),etc.),toxic anions(nitrate,phosphate,fluoride,etc.),and organic contaminants(organic dyes,antibiotics,etc.).These contributions demonstrate a deep understanding of the synergistic effect between the incorporated framework and homogeneous active centers.Besides,the challenges and perspectives of the future developments of ordered mesoporous materials in wastewater treatment are proposed.This work provides a theoretical basis and complete summary for the application of ordered mesoporous materials in the removal of contaminants from aqueous solutions.展开更多
The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added valu...The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.展开更多
A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state d...A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state depends on the thermal parameter,catalyzed photon number and squeezing parameter.We then analyze the nonclassical properties by examining the photon number distribution,photocount distribution and partial negativity of the Wigner function.Our findings indicate that nonclassicality can be achieved through the implementation of multiphoton catalysis operations and modulated by the thermal parameter,catalyzed photon number and squeezing parameter.展开更多
Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are ...Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are becoming popular materials because of their low cost, high electron conductivity, and controllable surface property. At the stage of catalysts preparation, the rational design of active sites is necessary for the substantial improvement of activity of catalysts. To date, the reported design strategies are mainly about synthesis mechanism and synthetic method. The level of understanding of design strategies of carbon-based single atom catalysts is requiring deep to be paved. The design strategies about manufacturing defects and coordination modulation of catalysts are presented. The design strategies are easy to carry out in the process of drawing up preparation routes. The components of carbon-based SACs can be divided into two parts: active site and carbon skeleton. In this review, the manufacture of defects and coordination modulation of two parts are introduced, respectively. The structure features and design strategies from the active sites and carbon skeletons to the overall catalysts are deeply discussed.Then, the structural design of different nano-carbon SACs is introduced systematically. The characterization of active site and carbon skeleton and the detailed mechanism of reaction process are summarized and analyzed. Next, the applications in the field of electrocatalysis for oxygen conversion and hydrogen conversion are illustrated. The relationships between the superior performance and the structure of active sites or carbon skeletons are discussed. Finally, the conclusion of this review and prospects on the abundant space for further promotion in broader fields are depicted. This review highlights the design and preparation thoughts from the parts to the whole. The detailed and systematic discussion will provide useful guidance for design of SACs for readers.展开更多
The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and deba...The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.展开更多
CO_(2) conversion into value-added products by electro-, photoand plasma catalysis under mild operating conditions(ambient temperature and pressure) is an emerging area to achieve carbon circularity by producing chemi...CO_(2) conversion into value-added products by electro-, photoand plasma catalysis under mild operating conditions(ambient temperature and pressure) is an emerging area to achieve carbon circularity by producing chemicals and fuels using directly renewable energy. Among all CO_(2) conversion approaches, the electrocatalytic reduction of CO_(2) is the most mature technology, capable of achieving high productivity(i.e. high current densities) at large scale, especially for producing carbon monoxide(CO), but with many examples showing selectivity to C_(2) carbon products.展开更多
Hard carbon draws great interests as anode material in lithium ion batteries （LIBs） due to its high the- oretical capacity, high rate capability and abundance of its precursors. Herein we firstly synthesize the lign...Hard carbon draws great interests as anode material in lithium ion batteries （LIBs） due to its high the- oretical capacity, high rate capability and abundance of its precursors. Herein we firstly synthesize the lignin-melamine resins by grafting melamine onto lignin. Afterwards, nitrogen doped hard carbon is pre- pared by the pyrolysis of lignin-melamine resins with the aid of catalyst （Ni（NO_3）2·6H_2O） at 1000 ℃. Compared with the samples without nitrogen-doping and catalysis, as-prepared nitrogen doped hard car- bon exhibits higher reversible capacity （345 mAh g-1 at 0.1 A g-1 ）, higher rate capability （145 mAh g-1 at 5 A g-1） and excellent cycling stability. The superior electrochemical performance is ascribed to the synergistic effect of nitrogen doping, graphitic structure and amorphous structure. Among them, nitro- gen doping could create the vacancies around the nitrogen sites, which enhance the reactivity and the electronic conductivity of materials. Additionally, graphitic structure also enhances the electronic con- ductivity of materials, thus improving the electrochemical performance of hard carbon. It is worthwhile that Iignin, renewable and abundant biopolymer, is converted to hard carbon with good electrochemical performance, which realizes the high value utilization of lignin.展开更多
Photothermal catalysis realizes the synergistic effect of solar energy and thermochemistry,which also has the potential to improve the reaction rate and optimize the selectivity.In this review,the research progress of...Photothermal catalysis realizes the synergistic effect of solar energy and thermochemistry,which also has the potential to improve the reaction rate and optimize the selectivity.In this review,the research progress of photothermal catalytic removal of volatile organic compounds(VOCs)by nano-catalysts in recent years is systematically reviewed.First,the fundamentals of photothermal catalysis and the fabrication of catalysts are described,and the design strategy of optimizing photothermal catalysis performance is proposed.Second,the performance for VOC degradation with photothermal catalysis is evaluated and compared for the batch and continuous systems.Particularly,the catalytic mechanism of VOC oxidation is systematically introduced based on experimental and theoretical study.Finally,the future limitations and challenges have been discussed,and potential research directions and priorities are highlighted.A broad view of recent photothermal catalyst fabrication,applications,challenges,and prospects can be systemically provided by this review.展开更多
Methane partial oxidation to methanol （MPOM） using dielectric barrier discharge over a Fe2O3-CuO/γ-Al2O3 catalyst was performed.The multicomponent catalyst was combined with plasma in two different configurations,i...Methane partial oxidation to methanol （MPOM） using dielectric barrier discharge over a Fe2O3-CuO/γ-Al2O3 catalyst was performed.The multicomponent catalyst was combined with plasma in two different configurations,i.e.,in-plasma catalysis （IPC） and post-plasma catalysis （PPC）.It was found that the catalytic performance of the catalysts for MPOM was strongly dependent on the hybrid configuration.A better synergistic performance of plasma and catalysis was achieved in the IPC configuration,but the catalysts packed in the discharge zone showed lower stability than those connected to the discharge zone in sequence.Active species,such as ozone,atomic oxygen and methyl radicals,were produced from the plasma-catalysis process,and made a major contribution to methanol synthesis.These active species were identified by the means of in situ optical emission spectra,ozone measurement and FT-IR spectra.It was confirmed that the amount of active species in the IPC system was greater than that in the PPC system.The results of TG,XRD,and N2 adsorption-desorption revealed that carbon deposition on the spent catalyst surface was responsible for the catalyst deactivation in the IPC configuration.展开更多
Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine ...Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.展开更多
In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and ch...In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and chemical stabilities.This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples.Then,the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis,including catalysis of the redox reactions,addition reactions,esterification reactions,Knoevenagel condensations,and hydrogenation-dehydrogenation reactions,has been elaborately discussed.Finally,we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.展开更多
It is well known that two-dimensional(2D)MXene-derived quan-tum dots(MQDs)inherit the excellent physicochemical properties of the parental MXenes,as a Chinese proverb says,“Indigo blue is extracted from the indigo pl...It is well known that two-dimensional(2D)MXene-derived quan-tum dots(MQDs)inherit the excellent physicochemical properties of the parental MXenes,as a Chinese proverb says,“Indigo blue is extracted from the indigo plant,but is bluer than the plant it comes from.”Therefore,0D QDs harvest larger surface-to-volume ratio,outstanding optical properties,and vigorous quantum confinement effect.Currently,MQDs trigger enormous research enthusiasm as an emerging star of functional materials applied to physics,chemistry,biology,energy conversion,and storage.Since the surface properties of small-sized MQDs include the type of surface functional groups,the functionalized surface directly determines their performance.As the Nobel Laureate Wolfgang Pauli says,“God made the bulk,but the surface was invented by the devil,”and it is just on the basis of the abundant surface functional groups,there is lots of space to be thereof excavated from MQDs.We are witnessing such excellence and even more promising to be expected.Nowadays,MQDs have been widely applied to catalysis,whereas the related reviews are rarely reported.Herein,we provide a state-of-the-art overview of MQDs in catalysis over the past five years,ranging from the origin and development of MQDs,synthetic routes of MQDs,and functionalized MQDs to advanced characterization techniques.To explore the diversity of catalytic application and perspectives of MQDs,our review will stimulate more efforts toward the synthesis of optimal MQDs and thereof designing high-performance MQDs-based catalysts.展开更多
The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocat...The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocatalysis,the thermal-driven catalysis(thermocatalysis) including liquid phase and gas phase reactions involves wider scope and is relatively easy to realize practical large-scale applications.Over the past several years,some striking achievements on the design of new carbon-based metal-free materials with well-defined structures and heteroatom groups as well as the revelation of new reaction mechanisms and active sites in thermocatalysis have been obtained.However,comparative discussions regarding these recent achievements have been rarely highlighted.In this review,we systematically summarize and discuss six kinds of carbocatalysts and their applications in thermocatalysis.These materials include typical oxygen-attached carbon,surface modified carbon(graft with certain organic compounds),mono-doped carbon,co-doped carbon,carbon nitride and materials with carbon as dopant.Some new reaction processes as well as the related reaction mechanisms,active sites and intermediates are reviewed critically.Moreover,an outlook on the in-depth investigation of the metalfree carbocatalysis in the future is provided.展开更多
We present a scheme for implementing locally a nonlocal N-target controlled–controlled gate with unit probability of success by harnessing two（N＋1）-qubit Greenberger–Horne–Zeilinger（GHZ） states as quantum chan...We present a scheme for implementing locally a nonlocal N-target controlled–controlled gate with unit probability of success by harnessing two（N＋1）-qubit Greenberger–Horne–Zeilinger（GHZ） states as quantum channel and N qutrits as catalyser. The quantum network that implements this nonlocal（N＋2）-body gate is built entirely of local single-body and two-body gates, and has only（3N＋2） two-body gates. This result suggests that both the computational depth of quantum network and the quantum resources required to perform this nonlocal gate might be significantly reduced. This scheme can be generalized straightforwardly to implement a nonlocal N-target and M-control qubits gate.展开更多
Lithium-sulfur(Li-S)batteries are hampered by the infamous shuttle effect and slow redox kinetics,resulting in rapid capacity decay.Herein,a bifunctional catalysis CoB/BN@rGO with integrated structure and synergy effe...Lithium-sulfur(Li-S)batteries are hampered by the infamous shuttle effect and slow redox kinetics,resulting in rapid capacity decay.Herein,a bifunctional catalysis CoB/BN@rGO with integrated structure and synergy effect between adsorption and catalysis is proposed to solve the above problems.The integrated CoB and BN are simultaneously and uniformly introduced on the rGO substrate through a one-step calcination strategy,applied to modify the cathode side of PP separator.The transition metal borides can catalyze the conversion of lithium polysulfides(Li_(2)Sn,n≥4),whereas the bond of B-S is too weak to absorb LPS.Thus BN introduced can effectively restrict the diffusion of polysulfides via strong chemisorption with LiSnLi+…N,while the rGO substrate ensures smooth electron transfer for redox reaction.Therefore,through the integrated adsorption/catalysis,the shuttle effect is suppressed,the kinetics of redox reaction is enhanced,and the capacity decay is reduced.Using CoB/BN@rGO modified PP separator,the Li-S batteries with high initial capacity(1450 mAh g^(-1)at 0.35 mA cm^(-2))and long-cycle stability(700 cycles at 1.74 mA cm^(-2)with a decay rate of 0.032%per cycle)are achieved.This work provides a novel insight for the preparation of bifunctional catalysis with integrated structure for long-life Li-S batteries.展开更多
Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because o...Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because of its high intrinsic activity and moderate cost.In this work,we examined the effect of BaNH,CaNH and Mg3 N2 on the catalytic activity of Co in the NH3 decomposition reaction.The H2 formation rate ranks the order as Co-BaNH>Co-CaNH>Co-Mg3 N2≈Co/CNTs within a reaction temperature range of 300-550℃.It is worth pointing out that the H2 formation rate of Co-BaNH at 500℃reaches20 mmolH2 gcat-1 min-1,which is comparable to those of the active Ru/Al2 O3(ca.17 mmolH2 gcat-1 min1)and Ru/AC(21 mmolH2 gcat-1 min-1)catalysts under the similar reaction conditions.In-depth research shows that Co-BaNH exhibits an obviously higher intrinsic activity and much lower Ea(46.2 kJ mol-1)than other Co-based catalysts,suggesting that BaNH may play a different role from CaNH,Mg3 N2 and CNTs during the catalytic process.Combined results of XRD,Ar-TPD and XAS show that a[Co-N-Ba]-like intermediate species is likely formed at the interface of Co metal and BaNH,which may lead to a more energy-efficient reaction pathway than that of neat Co metal for NH3 decomposition.展开更多
Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid p...Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.展开更多
Light-to-thermal conversion materials(LTCMs)have been of great interest to researchers due to their impressive energy conversion capacity and wide range of applications in biomedical,desalination,and synergistic catal...Light-to-thermal conversion materials(LTCMs)have been of great interest to researchers due to their impressive energy conversion capacity and wide range of applications in biomedical,desalination,and synergistic catalysis.Given the limited advances in existing materials(metals,semiconductors,π-conjugates),researchers generally adopt the method of constructing complex systems and hybrid structures to optimize performance and achieve multifunctional integration.However,the development of LTCMs is still in its infancy as the physical mechanism of light-to-thermal conversion is unclear.In this review,we proposed design strategies for efficient LTCMs by analyzing the physical process of light-tothermal conversion.First,we analyze the nature of light absorption and heat generation to reveal the physical processes of light-to-thermal conversion.Then,we explain the light-to-thermal conversion mechanisms of metallic,semiconducting andπ-conjugated LCTMs,and propose new material design strategies and performance improvement methods.Finally,we summarize the challenges and prospects of LTCMs in emerging applications such as solar water evaporation and photothermal catalysis.展开更多
Closing the carbon loop,through CO_(2)capture and utilization,is a promising route to mitigate climate change.Solar energy is a sustainable energy source which can be exploited to drive catalytic reactions for utilizi...Closing the carbon loop,through CO_(2)capture and utilization,is a promising route to mitigate climate change.Solar energy is a sustainable energy source which can be exploited to drive catalytic reactions for utilizing CO_(2),including converting the CO_(2)into useful products.Solar energy can be harnessed through a range of different pathways to valorize CO_(2).Whilst using solar energy to drive CO_(2)reduction has vast potential to promote catalytic CO_(2)conversions,the progress is limited due to the lack of understanding of property-performance relations as well as feasible material engineering approaches.Herein,we outline the various driving forces involved in photothermal CO_(2)catalysis.The heat from solar energy can be utilized to induce CO_(2)catalytic reduction reactions via the photothermal effect.Further,solar energy can act to modify reaction pathways through light-matter interactions.Light-induced chemical functions have demonstrated the ability to regulate intermediary reaction steps,and thus control the reaction selectivity.Photothermal catalyst structures and specific catalyst design strategies are discussed in this context.This review provides a comprehensive understanding of the heat-light synergy and guidance for rational photothermal catalyst design for CO_(2)utilization.展开更多
基金financially supported by National Key R&D Program of China(2021YFB3500702)National Natural Science Foundation of China(Nos.21677010 and 51808037)Special fund of Beijing Key Laboratory of Indoor Air Quality Evaluation and Control(No.BZ0344KF21-04).
文摘With the ongoing depletion of fossil fuels,energy and environmental issues have become increasingly critical,necessitating the search for effective solutions.Catalysis,being one of the hallmarks of modern industry,offers a promising avenue for researchers.However,the question of how to significantly enhance the performance of catalysts has gradually drawn the attention of scholars.Defect engineering,a commonly employed and effective approach to improve catalyst activity,has become a significant research focus in the catalysis field in recent years.Nonmetal vacancies have received extensive attention due to their simple form.Consequently,exploration of metal vacancies has remained stagnant for a considerable period,resulting in a scarcity of comprehensive reviews on this topic.Therefore,based on the latest research findings,this paper summarizes and consolidates the construction strategies for metal vacancies,characterization techniques,and their roles in typical energy and environmental catalytic reactions.Additionally,it outlines potential challenges in the future,aiming to provide valuable references for researchers interested in investigating metal vacancies.
基金supported by the National Natural Science Foundation of China(52370041)National Natural Science Foundation of China(21976134 and 21707104)State Key Laboratory of Pollution treatment and Resource Reuse Foundation(NO.PCRRK21001).
文摘To meet the growing emission of water contaminants,the development of new materials that enhance the efficiency of the water treatment system is urgent.Ordered mesoporous materials provide opportunities in environmental processing applications due to their exceptionally high surface areas,large pore sizes,and enough pore volumes.These properties might enhance the performance of materials concerning adsorption/catalysis capability,durability,and stability.In this review,we enumerate the ordered mesoporous materials as adsorbents/catalysts and their modifications in water pollution treatment from the past decade,including heavy metals(Hg^(2+),Pb^(2+),Cd^(2+),Cr^(6+),etc.),toxic anions(nitrate,phosphate,fluoride,etc.),and organic contaminants(organic dyes,antibiotics,etc.).These contributions demonstrate a deep understanding of the synergistic effect between the incorporated framework and homogeneous active centers.Besides,the challenges and perspectives of the future developments of ordered mesoporous materials in wastewater treatment are proposed.This work provides a theoretical basis and complete summary for the application of ordered mesoporous materials in the removal of contaminants from aqueous solutions.
基金supported by the National Key R&D Program of China (2018YFA0901700)National Natural Science Foundation of China (22278241)+1 种基金a grant from the Institute Guo Qiang, Tsinghua University (2021GQG1016)Department of Chemical Engineering-iBHE Joint Cooperation Fund。
文摘The increasing atmospheric carbon dioxide (CO_(2)) concentration has exposed a series of crises in the earth's ecological environment.How to effectively fix and convert carbon dioxide into products with added value has attracted the attention of many researchers.Cell-free enzyme catalytic system coupled with electrical and light have been a promising attempt in the field of biological carbon fixation in recent years.In this review,the research progresses of photoenzyme catalysis,electroenzyme catalysis and photo-electroenzyme catalysis for converting carbon dioxide into chemical products in cell-free systems are systematically summarized.We focus on reviewing and comparing various coupling methods and principles of photoenzyme catalysis and electroenzyme catalysis in cell-free systems,especially the materials used in the construction of the coupling system,and analyze and point out the characteristics and possible problems of different coupling methods.Finally,we discuss the major challenges and prospects of coupling physical signals and cell-free enzymatic catalytic systems in the field of CO_(2) fixation,suggesting possible strategies to improve the carbon sequestration capacity of such systems.
基金supported by the National Natural Science Foundation of China (Grant No.11347026)the Natural Science Foundation of Shandong Province,China (Grant Nos.ZR2020MA085 and ZR2020MF113)。
文摘A new kind of non-Gaussian quantum catalyzed state is proposed via multiphoton measurements and two-mode squeezing as an input of thermal state.The characteristics of the generated multiphoton catalysis output state depends on the thermal parameter,catalyzed photon number and squeezing parameter.We then analyze the nonclassical properties by examining the photon number distribution,photocount distribution and partial negativity of the Wigner function.Our findings indicate that nonclassicality can be achieved through the implementation of multiphoton catalysis operations and modulated by the thermal parameter,catalyzed photon number and squeezing parameter.
基金funded by the National Natural Science Foundation of China (Nos. 22279118, 31901272, 21401168, U1204203)National Science Fund for Distinguished Young of China (No. 22225202)+1 种基金Young Top Talent Program of Zhongyuan-YingcaiJihua (No. 30602674)Top-Notch Talent Program of Henan Agricultural University (No. 30501034)。
文摘Single atom catalysts(SACs) possessing regulated electronic structure, high atom utilization, and superior catalytic efficiency have been studied in almost all fields in recent years. Carbon-based supporting SACs are becoming popular materials because of their low cost, high electron conductivity, and controllable surface property. At the stage of catalysts preparation, the rational design of active sites is necessary for the substantial improvement of activity of catalysts. To date, the reported design strategies are mainly about synthesis mechanism and synthetic method. The level of understanding of design strategies of carbon-based single atom catalysts is requiring deep to be paved. The design strategies about manufacturing defects and coordination modulation of catalysts are presented. The design strategies are easy to carry out in the process of drawing up preparation routes. The components of carbon-based SACs can be divided into two parts: active site and carbon skeleton. In this review, the manufacture of defects and coordination modulation of two parts are introduced, respectively. The structure features and design strategies from the active sites and carbon skeletons to the overall catalysts are deeply discussed.Then, the structural design of different nano-carbon SACs is introduced systematically. The characterization of active site and carbon skeleton and the detailed mechanism of reaction process are summarized and analyzed. Next, the applications in the field of electrocatalysis for oxygen conversion and hydrogen conversion are illustrated. The relationships between the superior performance and the structure of active sites or carbon skeletons are discussed. Finally, the conclusion of this review and prospects on the abundant space for further promotion in broader fields are depicted. This review highlights the design and preparation thoughts from the parts to the whole. The detailed and systematic discussion will provide useful guidance for design of SACs for readers.
基金supported by the National Natural Science Foundation of China(U2032151,22272059)。
文摘The activity and selectivity of electrocatalytic CO_(2)reduction reaction(CO_(2)RR)to C_(2)products on metal catalysts can be regulated by molecular surfactants.However,the mechanism behind it remains elusive and debatable.Herein,copper nanowires(Cu NWs)were fabricated and decorated with cobalt phthalocyanine(CoPc).The electronic interaction between the Cu NWs,CoPc,CO_(2) and CO_(2)RR intermediates were explored by density functional theory(DFT)calculations.It was found that the selectivity and activity of CO_(2)RR towards C_(2)products on Cu NWs were considerably enhanced from 35.2%to 69.9%by surface decoration of CoPc.DFT calculations revealed that CO_(2)RR can proceed in the interphase between Cu substrate and CoPc,and the CO_(2)RR intermediates could synergistically bond with both Cu and Co metal centre in CuNWs-CoPc,which favours the adsorption of CO_(2),CO and CO_(2)RR intermediates,thus reducing the free energy for CO-COcoupling towards C_(2)products.The synergistic interaction was further extended to phthalocyanine(Pc)and other metal phthalocyanine derivatives(MPc),where a relatively weaker synergistic interaction of COintermediates with MPc and Cu substrate and only a slight enhancement of CO_(2)RR towards C_(2) products were observed.This study demonstrates a synergistic catalysis pathway for CO_(2)RR,a novel perspective in interpreting the role of CoPc in enhancing the activity and selectivity of CO_(2)RR on Cu NWs,in contrast to the conventional tandem catalysis mechanism.
文摘CO_(2) conversion into value-added products by electro-, photoand plasma catalysis under mild operating conditions(ambient temperature and pressure) is an emerging area to achieve carbon circularity by producing chemicals and fuels using directly renewable energy. Among all CO_(2) conversion approaches, the electrocatalytic reduction of CO_(2) is the most mature technology, capable of achieving high productivity(i.e. high current densities) at large scale, especially for producing carbon monoxide(CO), but with many examples showing selectivity to C_(2) carbon products.
基金financially supported by the Science and Technology research on strategic emerging industry of Hunan Province, China (Grant No. 2016GK4029)Shenzhen Greenway Technology Co., Ltd in China (No. H20150420035)the Fundamental Research Funds for the Central Universities of Central South University (No. 2017zzts126)
文摘Hard carbon draws great interests as anode material in lithium ion batteries （LIBs） due to its high the- oretical capacity, high rate capability and abundance of its precursors. Herein we firstly synthesize the lignin-melamine resins by grafting melamine onto lignin. Afterwards, nitrogen doped hard carbon is pre- pared by the pyrolysis of lignin-melamine resins with the aid of catalyst （Ni（NO_3）2·6H_2O） at 1000 ℃. Compared with the samples without nitrogen-doping and catalysis, as-prepared nitrogen doped hard car- bon exhibits higher reversible capacity （345 mAh g-1 at 0.1 A g-1 ）, higher rate capability （145 mAh g-1 at 5 A g-1） and excellent cycling stability. The superior electrochemical performance is ascribed to the synergistic effect of nitrogen doping, graphitic structure and amorphous structure. Among them, nitro- gen doping could create the vacancies around the nitrogen sites, which enhance the reactivity and the electronic conductivity of materials. Additionally, graphitic structure also enhances the electronic con- ductivity of materials, thus improving the electrochemical performance of hard carbon. It is worthwhile that Iignin, renewable and abundant biopolymer, is converted to hard carbon with good electrochemical performance, which realizes the high value utilization of lignin.
基金sponsored financially by the National Natural Science Foundation of China (No.21906104 and No.12175145)the Shanghai Rising-Star Program (21QA1406600).
文摘Photothermal catalysis realizes the synergistic effect of solar energy and thermochemistry,which also has the potential to improve the reaction rate and optimize the selectivity.In this review,the research progress of photothermal catalytic removal of volatile organic compounds(VOCs)by nano-catalysts in recent years is systematically reviewed.First,the fundamentals of photothermal catalysis and the fabrication of catalysts are described,and the design strategy of optimizing photothermal catalysis performance is proposed.Second,the performance for VOC degradation with photothermal catalysis is evaluated and compared for the batch and continuous systems.Particularly,the catalytic mechanism of VOC oxidation is systematically introduced based on experimental and theoretical study.Finally,the future limitations and challenges have been discussed,and potential research directions and priorities are highlighted.A broad view of recent photothermal catalyst fabrication,applications,challenges,and prospects can be systemically provided by this review.
基金supported by the National Natural Science Foundation of China(No. 20836008 and U0633003)the Zhejiang Provincial Natural Science Foundation of China(No. Y5080192)+3 种基金the Project of Science and Technology Department of Zhejiang Province of China(2007C13061)MOST Project of China(No. 2007AA06Z339,No. 2008BAC32B06 and No. 2007AA06A409)the Open Project Program of Key Laboratory of Non-point Sources Pollution Controlthe Ministry of Agriculture of the People’s Republic of China and Science Foundation of Chinese University
文摘Methane partial oxidation to methanol （MPOM） using dielectric barrier discharge over a Fe2O3-CuO/γ-Al2O3 catalyst was performed.The multicomponent catalyst was combined with plasma in two different configurations,i.e.,in-plasma catalysis （IPC） and post-plasma catalysis （PPC）.It was found that the catalytic performance of the catalysts for MPOM was strongly dependent on the hybrid configuration.A better synergistic performance of plasma and catalysis was achieved in the IPC configuration,but the catalysts packed in the discharge zone showed lower stability than those connected to the discharge zone in sequence.Active species,such as ozone,atomic oxygen and methyl radicals,were produced from the plasma-catalysis process,and made a major contribution to methanol synthesis.These active species were identified by the means of in situ optical emission spectra,ozone measurement and FT-IR spectra.It was confirmed that the amount of active species in the IPC system was greater than that in the PPC system.The results of TG,XRD,and N2 adsorption-desorption revealed that carbon deposition on the spent catalyst surface was responsible for the catalyst deactivation in the IPC configuration.
文摘Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.
基金financial support from the National Natural Science Foundation of China(22008032)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)+1 种基金the Shandong Provincial Natural Science Foundation(ZR2020ZD08)the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)
文摘In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and chemical stabilities.This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples.Then,the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis,including catalysis of the redox reactions,addition reactions,esterification reactions,Knoevenagel condensations,and hydrogenation-dehydrogenation reactions,has been elaborately discussed.Finally,we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.
基金supported by the National Natural Science Foundation of China(51872115,51932003)2020 International Cooperation Project of the Department of Science and Technology of Jilin Province(20200801001GH).
文摘It is well known that two-dimensional(2D)MXene-derived quan-tum dots(MQDs)inherit the excellent physicochemical properties of the parental MXenes,as a Chinese proverb says,“Indigo blue is extracted from the indigo plant,but is bluer than the plant it comes from.”Therefore,0D QDs harvest larger surface-to-volume ratio,outstanding optical properties,and vigorous quantum confinement effect.Currently,MQDs trigger enormous research enthusiasm as an emerging star of functional materials applied to physics,chemistry,biology,energy conversion,and storage.Since the surface properties of small-sized MQDs include the type of surface functional groups,the functionalized surface directly determines their performance.As the Nobel Laureate Wolfgang Pauli says,“God made the bulk,but the surface was invented by the devil,”and it is just on the basis of the abundant surface functional groups,there is lots of space to be thereof excavated from MQDs.We are witnessing such excellence and even more promising to be expected.Nowadays,MQDs have been widely applied to catalysis,whereas the related reviews are rarely reported.Herein,we provide a state-of-the-art overview of MQDs in catalysis over the past five years,ranging from the origin and development of MQDs,synthetic routes of MQDs,and functionalized MQDs to advanced characterization techniques.To explore the diversity of catalytic application and perspectives of MQDs,our review will stimulate more efforts toward the synthesis of optimal MQDs and thereof designing high-performance MQDs-based catalysts.
基金supported by the Award Program for Fujian Minjiang Scholar Professorship,the National Natural Science Foundation of China(21571035)Chemical Engineering&Technology of Zhejiang Province First-Class Discipline(Taizhou University),Zhejiang Provincial Natural Science Foundation of China(LQ20B060001)Taizhou science and technology planning project(1902gy20)。
文摘The carbon-based metal-free materials as catalysts(named as carbocatalysts) have been attracting tremendous attentions in electric-,solar-and thermal-driven reactions nowadays.Compared to electrocatalysis and photocatalysis,the thermal-driven catalysis(thermocatalysis) including liquid phase and gas phase reactions involves wider scope and is relatively easy to realize practical large-scale applications.Over the past several years,some striking achievements on the design of new carbon-based metal-free materials with well-defined structures and heteroatom groups as well as the revelation of new reaction mechanisms and active sites in thermocatalysis have been obtained.However,comparative discussions regarding these recent achievements have been rarely highlighted.In this review,we systematically summarize and discuss six kinds of carbocatalysts and their applications in thermocatalysis.These materials include typical oxygen-attached carbon,surface modified carbon(graft with certain organic compounds),mono-doped carbon,co-doped carbon,carbon nitride and materials with carbon as dopant.Some new reaction processes as well as the related reaction mechanisms,active sites and intermediates are reviewed critically.Moreover,an outlook on the in-depth investigation of the metalfree carbocatalysis in the future is provided.
基金Project supported by the Natural Science Foundation of Guangdong Province,China(Grant No.6029431)
文摘We present a scheme for implementing locally a nonlocal N-target controlled–controlled gate with unit probability of success by harnessing two（N＋1）-qubit Greenberger–Horne–Zeilinger（GHZ） states as quantum channel and N qutrits as catalyser. The quantum network that implements this nonlocal（N＋2）-body gate is built entirely of local single-body and two-body gates, and has only（3N＋2） two-body gates. This result suggests that both the computational depth of quantum network and the quantum resources required to perform this nonlocal gate might be significantly reduced. This scheme can be generalized straightforwardly to implement a nonlocal N-target and M-control qubits gate.
基金supported by the National Natural Science Foundation of China(22078228)。
文摘Lithium-sulfur(Li-S)batteries are hampered by the infamous shuttle effect and slow redox kinetics,resulting in rapid capacity decay.Herein,a bifunctional catalysis CoB/BN@rGO with integrated structure and synergy effect between adsorption and catalysis is proposed to solve the above problems.The integrated CoB and BN are simultaneously and uniformly introduced on the rGO substrate through a one-step calcination strategy,applied to modify the cathode side of PP separator.The transition metal borides can catalyze the conversion of lithium polysulfides(Li_(2)Sn,n≥4),whereas the bond of B-S is too weak to absorb LPS.Thus BN introduced can effectively restrict the diffusion of polysulfides via strong chemisorption with LiSnLi+…N,while the rGO substrate ensures smooth electron transfer for redox reaction.Therefore,through the integrated adsorption/catalysis,the shuttle effect is suppressed,the kinetics of redox reaction is enhanced,and the capacity decay is reduced.Using CoB/BN@rGO modified PP separator,the Li-S batteries with high initial capacity(1450 mAh g^(-1)at 0.35 mA cm^(-2))and long-cycle stability(700 cycles at 1.74 mA cm^(-2)with a decay rate of 0.032%per cycle)are achieved.This work provides a novel insight for the preparation of bifunctional catalysis with integrated structure for long-life Li-S batteries.
基金financial supports from the Project of the National Natural Science Foundation of China(Grant Nos.21633011and 21872137)“Transformational Technologies for Clean Energy and Demonstration”+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA21000000)Youth Innovation Promotion Association CAS(No.2018213)the Shanghai Synchrotron Radiation Facility(SSRF)for providing the beam time。
文摘Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because of its high intrinsic activity and moderate cost.In this work,we examined the effect of BaNH,CaNH and Mg3 N2 on the catalytic activity of Co in the NH3 decomposition reaction.The H2 formation rate ranks the order as Co-BaNH>Co-CaNH>Co-Mg3 N2≈Co/CNTs within a reaction temperature range of 300-550℃.It is worth pointing out that the H2 formation rate of Co-BaNH at 500℃reaches20 mmolH2 gcat-1 min-1,which is comparable to those of the active Ru/Al2 O3(ca.17 mmolH2 gcat-1 min1)and Ru/AC(21 mmolH2 gcat-1 min-1)catalysts under the similar reaction conditions.In-depth research shows that Co-BaNH exhibits an obviously higher intrinsic activity and much lower Ea(46.2 kJ mol-1)than other Co-based catalysts,suggesting that BaNH may play a different role from CaNH,Mg3 N2 and CNTs during the catalytic process.Combined results of XRD,Ar-TPD and XAS show that a[Co-N-Ba]-like intermediate species is likely formed at the interface of Co metal and BaNH,which may lead to a more energy-efficient reaction pathway than that of neat Co metal for NH3 decomposition.
基金financially supported by the Natural Science Foundation of Shandong Province,China(ZR2021QE192)the National Natural Science Foundation of China(21975154,22179078)+1 种基金the Postdoctoral Science Foundation of China(2018M63074)Qingdao Post-doctoral Applied Research Project(QDBSH20220202040)。
文摘Although lithium-sulfur batteries(Li SBs)are regarded as one of the most promising candidates for the next-generation energy storage system,the actual industrial application is hindered by the sluggish solid–liquid phase conversion kinetics,severe shuttle effect,and low sulfur loadings.Herein,a zeolitic imidazolate framework(ZIF)derived heterogeneous ZnSe-CoSe nanoparticles encapsulated in hollow N-doped carbon nanocage(ZnSe-CoSe-HNC)was designed by etching with tannic acid as a multifunctional electrocatalyst to boost the polysulfide conversion kinetics in LiSBs.The hollow structure in ZIF ensures large inner voids for sulfur and buffering volume expansions.Abundant exposed ZnSe-CoSe heterogeneous interfaces serve as bifunctional adsorption-catalytic centers to accelerate the conversion kinetics and alleviate the shuttle effect.Together with the highly conductive framework,the ZnSe-CoSeHNC/S cathode exhibits a high initial reversible capacity of 1305.3 m A h g-1at 0.2 C,high-rate capability,and reliable cycling stability under high sulfur loading and lean electrolyte(maintaining at 745 m A h g-1after 200 cycles with a high sulfur loading of 6.4 mg cm-2and a low electrolyte/sulfur ratio of 6μL mg^(-1)).Theoretical calculations have demonstrated the heterostructures of ZnSe-CoSe offer higher binding energy to lithium polysulfides than that of ZnSe or CoSe,facilitating the electron transfer to lithium polysulfides.This work provides a novel heterostructure with superior catalytic ability and hollow conductive architecture,paving the way for the practical application of functional sulfur electrodes.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.52272153,52032004)the KLOMT Key Laboratory Open Project(2022KLOMT02-05)。
文摘Light-to-thermal conversion materials(LTCMs)have been of great interest to researchers due to their impressive energy conversion capacity and wide range of applications in biomedical,desalination,and synergistic catalysis.Given the limited advances in existing materials(metals,semiconductors,π-conjugates),researchers generally adopt the method of constructing complex systems and hybrid structures to optimize performance and achieve multifunctional integration.However,the development of LTCMs is still in its infancy as the physical mechanism of light-to-thermal conversion is unclear.In this review,we proposed design strategies for efficient LTCMs by analyzing the physical process of light-tothermal conversion.First,we analyze the nature of light absorption and heat generation to reveal the physical processes of light-to-thermal conversion.Then,we explain the light-to-thermal conversion mechanisms of metallic,semiconducting andπ-conjugated LCTMs,and propose new material design strategies and performance improvement methods.Finally,we summarize the challenges and prospects of LTCMs in emerging applications such as solar water evaporation and photothermal catalysis.
基金supported by the Australian Research Council(ARC)under the Laureate Fellowship Scheme-FL140100081 and ARC Discovery Project DP170102410the support of Scientia Ph D Scholarship from UNSW Sydneythe support of Australia Government Research Training Program(RTP)Scholarship。
文摘Closing the carbon loop,through CO_(2)capture and utilization,is a promising route to mitigate climate change.Solar energy is a sustainable energy source which can be exploited to drive catalytic reactions for utilizing CO_(2),including converting the CO_(2)into useful products.Solar energy can be harnessed through a range of different pathways to valorize CO_(2).Whilst using solar energy to drive CO_(2)reduction has vast potential to promote catalytic CO_(2)conversions,the progress is limited due to the lack of understanding of property-performance relations as well as feasible material engineering approaches.Herein,we outline the various driving forces involved in photothermal CO_(2)catalysis.The heat from solar energy can be utilized to induce CO_(2)catalytic reduction reactions via the photothermal effect.Further,solar energy can act to modify reaction pathways through light-matter interactions.Light-induced chemical functions have demonstrated the ability to regulate intermediary reaction steps,and thus control the reaction selectivity.Photothermal catalyst structures and specific catalyst design strategies are discussed in this context.This review provides a comprehensive understanding of the heat-light synergy and guidance for rational photothermal catalyst design for CO_(2)utilization.
