Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalys...Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.展开更多
Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples w...Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples were characterized by means of various techniques, and their catalytic activities for HCHO(0.2%) oxidation were evaluated. Among the samples, Cu/Na Sep exhibited superior performance, and complete HCHO conversion was achieved at 100 ℃(GHSV = 240000 m L/(g·h)). Additionally, the sample retained good catalytic activity during a 42 h stability test. A number of factors, including elevated acidity, the abundance of oxygen species, and favorable low-temperature reducibility, were responsible for the excellent catalytic activity of Cu/Na Sep. According to the results of the in-situ DRIFTS characterization, the HCHO oxidation mechanism was as follows:(i) HCHO was rapidly decomposed into dioxymethylene(DOM) species on the Cu/Na Sep surface;(ii) DOM was then immediately converted to formate species;(iii) the resultant formate species were further oxidized to carbonates;(iv) the carbonate species were eventually converted to CO2 and H2O.展开更多
The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundame...The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundamental understanding of the nature of active sites and structure–performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection.This review surveys the effects of multiple factors,including the metal size,shape,support,alloy and ligand modifier,on the coordinated environment of active center and further their influence on the catalytic reactions,aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance.Subsequently,the key structure characterization techniques in determining the coordination structure of active metal sites,especially the dynamic coordination structure change under the reaction condition,are well summarized.A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.展开更多
Among the various types of heterogeneous catalysts,supported metal nanocatalysts(SMNCs)have attracted widespread interest in chemistry and materials science,due to their advantageous features,such as high efficiency,s...Among the various types of heterogeneous catalysts,supported metal nanocatalysts(SMNCs)have attracted widespread interest in chemistry and materials science,due to their advantageous features,such as high efficiency,stability,and reusability for catalytic reactions.However,to obtain well-defined SMNCs and inhibit nanoparticle aggregation,traditional approaches generally involve numerous organic reagents,complex steps,and specialized equipment,thus hindering the practical and large-scale synthesis of SMNCs.In this review,we summarize green and sustainable synthetic methodologies for the assembly of SMNCs,including low temperature pyrolysis and solid-state,surfactant-and reductant-free,and ionic liquid assisted syntheses.The conventional application of SMNCs for electrochemical hydrogen evolution and the corresponding achievements are subsequently discussed.Finally,future perspectives toward the sustainable production of SMNCs are presented.展开更多
LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a tw...LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation. The structure evolution of the sample as prepared was investigated by XRD, TPR and TEM techniques. For the former, the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNixO3. After reduction and reaction of CO methanation, its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3, in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell. For the latter, the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation, its chemical composites change to Ni/LaFeO3. Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition. In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor with different preparing method or preparing condition. Therefore, it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.展开更多
A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 （x = 0.03, 0.05, 0.07, 0.09, and 0.10） were prepared through a simple method of ci...A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 （x = 0.03, 0.05, 0.07, 0.09, and 0.10） were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.展开更多
Bi-metallic(Pt–Sn and Sn–Ni) and tri-metallic(Pt–Sn–Ni) catalysts,supported on Al-containing hexagonal mesoporous silica(Al-HMS)(Si/Al = 20) materials,were synthesized.N_2 adsorption–desorption,X-ray diffraction(...Bi-metallic(Pt–Sn and Sn–Ni) and tri-metallic(Pt–Sn–Ni) catalysts,supported on Al-containing hexagonal mesoporous silica(Al-HMS)(Si/Al = 20) materials,were synthesized.N_2 adsorption–desorption,X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET) test,and temperature programed desorption(NH3-TPD)were used to characterize physicochemical characteristics and textural properties of the Al-HMS catalysts.Catalytic performances on hydro-cracking of n-decane at different reaction conditions were studied in a microreactor.Comparison between Pt–Sn,Sn–Ni and Pt–Sn–Ni catalyst under different hydro-cracking conditions was made.The experimental results indicate that the proper balance between the acid and metal functions is the key in synthesizing a catalyst with a better performance in hydro-cracking.Tri-metallic catalyst exhibits the best catalytic performance in n-decane hydro-cracking than two bi-metallic catalysts.展开更多
Catalytic degradation of cellulose to chemicals is an attracting topic today for the conver- sion of biomass, and the development of novel catalysts is a key point. Since metal-organic frameworks （MOFs） possess unif...Catalytic degradation of cellulose to chemicals is an attracting topic today for the conver- sion of biomass, and the development of novel catalysts is a key point. Since metal-organic frameworks （MOFs） possess uniform, continuous, and permeable channels, they are valu- able candidate as catalysts. Here, a new 3D MOF/graphene catalyst was prepared by in situ growth of the zeolitic imidazolate frameworks （ZIF-8） nanoparticles inside the pore of an as-formed 3D reduced graphene oxide （rGO） hydrogel. The ZIF-8/rGO nanocomposite owns both micropores and mesopores with large specific surface area and plenty of acids sites, which is an idea catalyst for biomass degradation. Cellulose was dissolved in allmline aqueous solution at first, and then it was degraded efficiently over the new catalyst under hydrothermal condition. The conversion reaches 100% while the main products are formic acid with a maximum yield of 93.66%. In addition, the catalyst can be reused with high activity.展开更多
The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate （[C4mim]C1/FeCl3; Z = 0.5） proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of β-keto esters a...The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate （[C4mim]C1/FeCl3; Z = 0.5） proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of β-keto esters and enones. Due to the ionic structure of the catalyst, a significant acceleration of the reaction rate was observed under microwave conditions. Furthermore, recycling of the ionic liquid catalyst could be performed after simply distilling off the products.展开更多
A unique Pd＆Cu@Al catalyst was easily fabricated just by immersing commercial aluminum foil in a mixed xylene solution of PdC12 and CuCl2. The catalyst fabrication process led to aluminum oxide coatings in situ, whic...A unique Pd＆Cu@Al catalyst was easily fabricated just by immersing commercial aluminum foil in a mixed xylene solution of PdC12 and CuCl2. The catalyst fabrication process led to aluminum oxide coatings in situ, which supported the metal nanoparticles and enhanced their catalytic activities for the phosphine-free Heck reaction of awl halides and styrenes with high turnover number （TON） up to 3.9×10^5. The reaction can be scaled up to at least 100 mmol and has been applied in modification of drug Lapatinib＇s intermediate with low metal residue. This novel catalyst is of good application potential in industrial production because it was extremely easy to be recycled, in regardless of the generation of the insoluble impurities or tars during the reaction processes.展开更多
Since Haruta et al. discovered that small gold nanoparticles finely dispersed on certain metal oxide supports can exhibit surprisingly high activity in CO oxidation below room temperature, heterogeneous catalysis by s...Since Haruta et al. discovered that small gold nanoparticles finely dispersed on certain metal oxide supports can exhibit surprisingly high activity in CO oxidation below room temperature, heterogeneous catalysis by supported gold nanoparticles has attracted tremendous attention. The majority of publications deal with the preparation and characterization of conventional gold catalysts （e.g., Au/TiO2）, the use of gold catalysts in various catalytic reactions, as well as elucidation of the nature of the active sites and reaction mechanisms. In this overview, we highlight the development of novel supported gold catalysts from a materials perspective. Examples, mostly from those reported by our group, are given concerning the development of simple gold catalysts with single metal-support interfaces and heterostructured gold catalysts with complicated interfacial structures. Catalysts in the first category include active Au/SiO2 and Au/metal phosphate catalysts, and those in the second category include catalysts prepared by pre-modification of supports before loading gold, by post-modification of supported gold catalysts, or by simultaneous dispersion of gold and an inorganic component onto a support. CO oxidation has generally been employed as a probe reaction to screen the activities of these catalysts. These novel gold catalysts not only provide possibilities for applied catalysis, but also furnish grounds for fundamental research.展开更多
基金supported by the National High Technology Research and Development Program (863 Program,2015AA034603)the National Natural Science Foundation of China (21377008,201077007,20973017)+1 种基金Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal InstitutionsScientific Research Base Construction-Science and Technology Creation Platform National Materials Research Base Construction~~
文摘Most of volatile organic compounds （VOCs） are harmful to the atmosphere and human health. Cata‐lytic combustion is an effective way to eliminate VOCs. The key issue is the availability of high per‐formance catalysts. Many catalysts including transition metal oxides, mixed metal oxides, and sup‐ported noble metals have been developed. Among these catalysts, the porous ones attract much attention. In this review, we focus on recent advances in the synthesis of ordered mesoporous and macroporous transition metal oxides, perovskites, and supported noble metal catalysts and their catalytic oxidation of VOCs. The porous catalysts outperformed their bulk counterparts. This excel‐lent catalytic performance was due to their high surface areas, high concentration of adsorbed oxy‐gen species, low temperature reducibility, strong interaction between noble metal and support and highly dispersed noble metal nanoparticles and unique porous structures. Catalytic oxidation of carbon monoxide over typical catalysts was also discussed. We made conclusive remarks and pro‐posed future work for the removal of VOCs.
文摘Sodium-treated sepiolite(Na Sep)-supported transition metal catalysts(TM/Na Sep;TM = Cu, Fe, Ni, Mn, and Co) were synthesized via a rotary evaporation method. Physicochemical properties of the as-synthesized samples were characterized by means of various techniques, and their catalytic activities for HCHO(0.2%) oxidation were evaluated. Among the samples, Cu/Na Sep exhibited superior performance, and complete HCHO conversion was achieved at 100 ℃(GHSV = 240000 m L/(g·h)). Additionally, the sample retained good catalytic activity during a 42 h stability test. A number of factors, including elevated acidity, the abundance of oxygen species, and favorable low-temperature reducibility, were responsible for the excellent catalytic activity of Cu/Na Sep. According to the results of the in-situ DRIFTS characterization, the HCHO oxidation mechanism was as follows:(i) HCHO was rapidly decomposed into dioxymethylene(DOM) species on the Cu/Na Sep surface;(ii) DOM was then immediately converted to formate species;(iii) the resultant formate species were further oxidized to carbonates;(iv) the carbonate species were eventually converted to CO2 and H2O.
文摘The structural complexity of supported metal catalysts,playing significant role in a wide range of chemical technologies,have prevented us from deeply understanding their catalytic mechanisms at atomic level.A fundamental understanding of the nature of active sites and structure–performance relationship of supported metal catalysts from a comprehensive view will open up numerous new opportunities for the development of advanced catalysts to address the global challenges in energy conversion and environmental protection.This review surveys the effects of multiple factors,including the metal size,shape,support,alloy and ligand modifier,on the coordinated environment of active center and further their influence on the catalytic reactions,aiming to provide guidance for the design of industrialized heterogeneous catalysts with extraordinary performance.Subsequently,the key structure characterization techniques in determining the coordination structure of active metal sites,especially the dynamic coordination structure change under the reaction condition,are well summarized.A brief summary is finally provided together with personal perspectives on the further development in the field of heterogeneous metal catalysts.
文摘Among the various types of heterogeneous catalysts,supported metal nanocatalysts(SMNCs)have attracted widespread interest in chemistry and materials science,due to their advantageous features,such as high efficiency,stability,and reusability for catalytic reactions.However,to obtain well-defined SMNCs and inhibit nanoparticle aggregation,traditional approaches generally involve numerous organic reagents,complex steps,and specialized equipment,thus hindering the practical and large-scale synthesis of SMNCs.In this review,we summarize green and sustainable synthetic methodologies for the assembly of SMNCs,including low temperature pyrolysis and solid-state,surfactant-and reductant-free,and ionic liquid assisted syntheses.The conventional application of SMNCs for electrochemical hydrogen evolution and the corresponding achievements are subsequently discussed.Finally,future perspectives toward the sustainable production of SMNCs are presented.
基金supported by the Financial support from the NSF of China(21066007)the NSF of Tianjin China(10JCZDJC23800)the NSF of Mongolia China(2009BS0203)
文摘LaFeO3 perovskite supported Ni and Ni-Fe catalysts were prepared and applied to methanation reaction of syngas. Two preparation methods were employed. One was one-step citrate complexing method, and the other was a two step method using citrate complexing method to produce LaFeO3 and followed by loading nickel oxide on it with impregnation. The structure evolution of the sample as prepared was investigated by XRD, TPR and TEM techniques. For the former, the chemical composites of the calcined sample are NiO-Fe2O3/LaFe1-xNixO3. After reduction and reaction of CO methanation, its composites convert to Fe-Ni@Ni/LaFeO3-La2O2CO3, in which Fe-Ni@Ni is metal particles in nano-size composed of nickel core and Fe-Ni alloy shell. For the latter, the chemical composites of the calcined sample are NiO/LaFeO3; and after reduction and reaction of CO methanation, its chemical composites change to Ni/LaFeO3. Ni/LaFeO3 catalyst is a little more active, while Fe-Ni@Ni/LaFeO3-La2O2CO3 is much more stable and shows very good resistance to carbon deposition. In this work it is aimed to show that the structure and composites of the catalysts can be tailored using perovskite-type oxide as precursor with different preparing method or preparing condition. Therefore, it is a promising route to prepare supported bi-metal catalysts in nano-size for a lot of metals with desired catalytic performances.
基金supported by the National Natural Science Foundation of China(Nos.21576192,21776214)
文摘A new scheme for the preparation of highly dispersed precious metal catalysts is proposed in this work. Samples of LaCol-xPtxO3/SiO2 （x = 0.03, 0.05, 0.07, 0.09, and 0.10） were prepared through a simple method of citrate acid complexa-tion combined with impregnation. In a nanocrystallite of LaCOl-xPtxO3, ions of lanthanum, cobalt, and platinum are evenly mixed at the atomic level and confined within the nanocrystallite. In the reduction process, platinum ions were reduced and migrated onto the surface of the nanocrystallite, and the platinum should be highly dispersed owing to the even mixing of the platinum ions in the precursor. When x = 0.05 or lower, the highest dispersion of Pt could be achieved. The highly dispersed Pt is stable, because of the strong interaction between Pt atoms and the support. The catalysts were characterized by BET surface area, temperature-programmed reduction, X-ray diffraction, transmission electron microscopy, CO temperature-programmed desorption, and turnover frequency. Compared with general precious metal Pt catalysts, the LaCo0.95Pt0.05O3/ SiO2 catalyst exhibited better activity for CO oxidation, and it maintained stability at a high temperature of 400 ℃ for 250 h with complete CO conversion.
文摘Bi-metallic(Pt–Sn and Sn–Ni) and tri-metallic(Pt–Sn–Ni) catalysts,supported on Al-containing hexagonal mesoporous silica(Al-HMS)(Si/Al = 20) materials,were synthesized.N_2 adsorption–desorption,X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET) test,and temperature programed desorption(NH3-TPD)were used to characterize physicochemical characteristics and textural properties of the Al-HMS catalysts.Catalytic performances on hydro-cracking of n-decane at different reaction conditions were studied in a microreactor.Comparison between Pt–Sn,Sn–Ni and Pt–Sn–Ni catalyst under different hydro-cracking conditions was made.The experimental results indicate that the proper balance between the acid and metal functions is the key in synthesizing a catalyst with a better performance in hydro-cracking.Tri-metallic catalyst exhibits the best catalytic performance in n-decane hydro-cracking than two bi-metallic catalysts.
文摘Catalytic degradation of cellulose to chemicals is an attracting topic today for the conver- sion of biomass, and the development of novel catalysts is a key point. Since metal-organic frameworks （MOFs） possess uniform, continuous, and permeable channels, they are valu- able candidate as catalysts. Here, a new 3D MOF/graphene catalyst was prepared by in situ growth of the zeolitic imidazolate frameworks （ZIF-8） nanoparticles inside the pore of an as-formed 3D reduced graphene oxide （rGO） hydrogel. The ZIF-8/rGO nanocomposite owns both micropores and mesopores with large specific surface area and plenty of acids sites, which is an idea catalyst for biomass degradation. Cellulose was dissolved in allmline aqueous solution at first, and then it was degraded efficiently over the new catalyst under hydrothermal condition. The conversion reaches 100% while the main products are formic acid with a maximum yield of 93.66%. In addition, the catalyst can be reused with high activity.
基金financially supported by the Hochschuljubil umsstiftung der Stadt Wien
文摘The iron containing ionic liquid 1-butyl-3-methylimidazolium tetrachloroferrate （[C4mim]C1/FeCl3; Z = 0.5） proved to be an efficient catalyst for the solvent-free metal catalyzed Michael addition of β-keto esters and enones. Due to the ionic structure of the catalyst, a significant acceleration of the reaction rate was observed under microwave conditions. Furthermore, recycling of the ionic liquid catalyst could be performed after simply distilling off the products.
基金supported by the National Natural Science Foundation of China (21202141)Priority Academic Program Development (PAPD) of Jiangsu Higher Education Institutions+3 种基金the Young Science and Technology Talent Support Project of Jiangsu Province (Lei Yu)the High Level Talent Support Project of Yangzhou University (Topnotch Talent, Lei Yu)the Open Project Program of Jiangsu Key Laboratory of Zoonosis (R1509)the Testing Centre of Yangzhou University
文摘A unique Pd＆Cu@Al catalyst was easily fabricated just by immersing commercial aluminum foil in a mixed xylene solution of PdC12 and CuCl2. The catalyst fabrication process led to aluminum oxide coatings in situ, which supported the metal nanoparticles and enhanced their catalytic activities for the phosphine-free Heck reaction of awl halides and styrenes with high turnover number （TON） up to 3.9×10^5. The reaction can be scaled up to at least 100 mmol and has been applied in modification of drug Lapatinib＇s intermediate with low metal residue. This novel catalyst is of good application potential in industrial production because it was extremely easy to be recycled, in regardless of the generation of the insoluble impurities or tars during the reaction processes.
文摘Since Haruta et al. discovered that small gold nanoparticles finely dispersed on certain metal oxide supports can exhibit surprisingly high activity in CO oxidation below room temperature, heterogeneous catalysis by supported gold nanoparticles has attracted tremendous attention. The majority of publications deal with the preparation and characterization of conventional gold catalysts （e.g., Au/TiO2）, the use of gold catalysts in various catalytic reactions, as well as elucidation of the nature of the active sites and reaction mechanisms. In this overview, we highlight the development of novel supported gold catalysts from a materials perspective. Examples, mostly from those reported by our group, are given concerning the development of simple gold catalysts with single metal-support interfaces and heterostructured gold catalysts with complicated interfacial structures. Catalysts in the first category include active Au/SiO2 and Au/metal phosphate catalysts, and those in the second category include catalysts prepared by pre-modification of supports before loading gold, by post-modification of supported gold catalysts, or by simultaneous dispersion of gold and an inorganic component onto a support. CO oxidation has generally been employed as a probe reaction to screen the activities of these catalysts. These novel gold catalysts not only provide possibilities for applied catalysis, but also furnish grounds for fundamental research.
