Ni@Pd core-shell nanoparticles with a mean particle size of 8–9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine.Subsequently,the first-ever deposition o...Ni@Pd core-shell nanoparticles with a mean particle size of 8–9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine.Subsequently,the first-ever deposition of Ni@Pd core-shell nanoparticles having different compositions on a metal-organic framework（MIL-101）was accomplished by wet impregnation in n-hexane.The Ni@Pd/MIL-101 materials were characterized by powder X-ray diffraction,Fourier transform infrared spectroscopy,transmission electron microscopy,and energy-dispersive X-ray spectroscopy and also investigated as catalysts for the hydrogenation of nitrobenzene under mild reaction conditions.At 30 °C and 0.1 MPa of H2 pressure,the Ni@Pd/MIL-101 gives a TOF as high as 375 h–1 for the hydrogenation of nitrobenzene and is applicable to a wide range of substituted nitroarenes.The exceptional performance of this catalyst is believed to result from the significant Ni-Pd interaction in the core-shell structure,together with promotion of the conversions of aromatics by uncoordinated Lewis acidic Cr sites on the MIL-101 support.展开更多
Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with no...Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/ proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu1.94S-Zn0.23Cd0.775 semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.展开更多
An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors andα-Fe2O3 as a support.The catalyst with Pt content as low as 0.2 wt%exhibits high activities,c...An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors andα-Fe2O3 as a support.The catalyst with Pt content as low as 0.2 wt%exhibits high activities,chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes.The conversion of nitrobenzene can reach 3170 molconv h^–1 molPt^–1 under mild conditions(30°C,5 bar),which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions.The spatial separation of the active sites for H2 dissociation and hydrogenation should be responsible for the high chemoselectivity,which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles.The unique surface properties ofα-Fe2O3 play an important role in the reaction process.It provides active sites for hydrogen spillover and reactant adsorption,and ultimately completes the hydrogenation of the nitro group on the catalyst surface.展开更多
A facile,gram-scale and sustainable approach has been established for the synthesis of single-atomic-site iron on N-doped carbon(Fe_(SA)@NC-20A)via the pyrolysis of aniline modified FeZn-ZIFs,in which the synthesis of...A facile,gram-scale and sustainable approach has been established for the synthesis of single-atomic-site iron on N-doped carbon(Fe_(SA)@NC-20A)via the pyrolysis of aniline modified FeZn-ZIFs,in which the synthesis of zeolitic imidazolate frameworks(ZIFs)can be accomplished in water at room temperature,and no acid etching is required.The as-synthesized catalyst exhibits better performance on the chemoselective hydrogenation of nitroarenes with a broad substrate scope(turnover frequency(TOF)up to 1,727 h^(-1),23 examples)than most of previously reported works.Based on high-angle annular dark field scanning transmission microscopy(HAADF-STEM)images in combination with X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),electron spin resonance(ESR),and Mossbauer spectroscopy,Fe is dispersed as single atoms via forming FeNx(x=4-6).This work not only determines the active sites of FesA@NC-20A for hydrogenation(FeN4),but also proposes tentative pathways for both N-H activation of hydrazine and the reduction of nitroarene on FeN4 site,both of which are the key steps for the hydrogenation of nitroarenes.In addition,this catalyst shows excellent stability,and no significant activity degradation is observed when recycling for 10 times or restoring in air for 2 months.展开更多
Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were...Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were embedded into carbon films,was prepared via the pyrolysis of iron‐polyaniline complexes on carbon particles.The obtained catalyst shows a large surface area,uniform pore channel distribution,with the Fe2O3NPs homogeneously dispersed across the hybrid material.Scanning electron microscopy,Raman spectroscopy and X‐ray diffraction analyses of the catalyst prepared at900°C(Fe2O3@G‐C‐900)and an acid‐pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles.Observation of high‐resolution transmission electron microscopy images also revealed that the Fe2O3NPs in the hybrid were encapsulated by a thin carbon film.The Fe2O3@G‐C‐900composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions,where previously noble metals were required.The synthetic strategy and the structure of the iron oxide‐based composite may lead to the advancement of cost‐effective and sustainable industrial processes.展开更多
We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst（O-MoS2）.O-MoS2 was prepared by incomplete sul idation and reduction...We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst（O-MoS2）.O-MoS2 was prepared by incomplete sul idation and reduction of an ammonium molybdate precursor.A number of Mo-O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets.As a consequence of the different coordination geometries of O（Mo O2） and S（MoS2）,and lengths of the Mo-O and Mo-S bonds,the implanted Mo-O bonds induced obvious defects and more coordinatively unsaturated（CUS） Mo sites in O-MoS2,as confirmed by X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,high resolution transmission electron microscopy,and extended X-ray absorption fine structure characterization of various MoS2-based materials.O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.展开更多
Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and ...Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and reactants.Herein,we report efficient adjustment of the product selectivity in the hydrogenation of substituted nitroarenes via rational reaction intermediates achieved using controllable Pd nanoparticles.Pd nanoparticles fixed within zeolite Beta crystals(Pd@Beta)afforded rational Pd-NO2 interactions,in which the Pd nanoparticle-adsorbed substituted nitroarenes,such as nitrobenzaldehyde,were reasonably hydrogenated into the corresponding aminobenzaldehyde.However,for Pd nanoparticles supported on the external surfaces of zeolite beta crystals,various side products were obtained owing to the coexistence of Pd-NO2 and Pd-C=O interactions.When Pd nanoparticles were artificially controlled in various positions in a fixed-bed reactor,the product selectivity was significantly affected.These results demonstrate the importance of molecular adsorption and diffusion processes in adjusting product selectivity in catalytic reactions.展开更多
In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐source...In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐sourced reducing agent,without stabilizers or surfactants.This synthetic process is environmentally‐friendly and avoids the use of toxic reducing agents.Phenolic hydroxyl groups in the leaf extract are believed to reduce Cu2+in solution to generate Cu NPs that are subsequently stabilized on the MnO2NP surfaces.The resulting Cu/MnO2nanocomposite was fully characterized using X‐ray diffraction,transmission electron microscopy,field emission scanning electron microscopy,energy‐dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy.This material was found to function as a highly active,efficient and recyclable heterogeneous catalyst for the reduction of Congo red,rhodamine B and methylene blue as well as nitro compounds such as2,4‐dinitrophenylhydrazine and4‐nitrophenol in the presence of NaBH4in aqueous media at ambient temperature.The high stability of the Cu/MnO2nanocomposite also allows the catalyst to be separated and reused several times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
基金supported by the National Natural Science Foundation of China(21322606 and 21436005)the Specialized Research Fund for the Doctoral Program of Higher Education(20120172110012)+1 种基金the Fundamental Research Funds for the Central Universitiesthe Natural Science Foundation of Guangdong Province(S2011020002397 and 2013B090500027)~~
文摘Ni@Pd core-shell nanoparticles with a mean particle size of 8–9 nm were prepared by solvothermal reduction of bivalent nickel and palladium in oleylamine and trioctylphosphine.Subsequently,the first-ever deposition of Ni@Pd core-shell nanoparticles having different compositions on a metal-organic framework（MIL-101）was accomplished by wet impregnation in n-hexane.The Ni@Pd/MIL-101 materials were characterized by powder X-ray diffraction,Fourier transform infrared spectroscopy,transmission electron microscopy,and energy-dispersive X-ray spectroscopy and also investigated as catalysts for the hydrogenation of nitrobenzene under mild reaction conditions.At 30 °C and 0.1 MPa of H2 pressure,the Ni@Pd/MIL-101 gives a TOF as high as 375 h–1 for the hydrogenation of nitrobenzene and is applicable to a wide range of substituted nitroarenes.The exceptional performance of this catalyst is believed to result from the significant Ni-Pd interaction in the core-shell structure,together with promotion of the conversions of aromatics by uncoordinated Lewis acidic Cr sites on the MIL-101 support.
基金We thank the National Natural Science Foundation of China for support （Nos. 21325101, 21231005, and 21171105） and China Ministry of Science and Technology under Contract of 2016YFA （No. 0202801）.
文摘Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/ proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu1.94S-Zn0.23Cd0.775 semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.
基金supported by the National Natural Science Foundation of China(21473073,21473074)‘‘13th Five-Year’’ Science and Technology Research of the Education Department of Jilin Province(2016403)+1 种基金the Development Project of Science and Technology of Jilin Province(20170101171JC,20180201068SF)the Open Project of State Key Laboratory of Inorganic Synthesis and Preparative Chemistry(201703)~~
文摘An efficient and low-cost supported Pt catalyst for hydrogenation of niroarenes was prepared with colloid Pt precursors andα-Fe2O3 as a support.The catalyst with Pt content as low as 0.2 wt%exhibits high activities,chemoselectivities and stability in the hydrogenation of nitrobenzene and a variety of niroarenes.The conversion of nitrobenzene can reach 3170 molconv h^–1 molPt^–1 under mild conditions(30°C,5 bar),which is much higher than that of commercial Pt/C catalyst and many reported catalysts under similar reaction conditions.The spatial separation of the active sites for H2 dissociation and hydrogenation should be responsible for the high chemoselectivity,which decreases the contact possibility between the reducible groups of nitroarenes and Pt nanoparticles.The unique surface properties ofα-Fe2O3 play an important role in the reaction process.It provides active sites for hydrogen spillover and reactant adsorption,and ultimately completes the hydrogenation of the nitro group on the catalyst surface.
基金the Fundamental Research Funds for the Central Universities(No.30920021120)the Key Laboratory of Biomass Energy and Material,Jiangsu Province(No.JSBEM201912)+1 种基金the National Natural Science Foundation of China(No.21905089)the Chinese Postdoctoral Science Foundation(No.2019M662775)for financial support。
文摘A facile,gram-scale and sustainable approach has been established for the synthesis of single-atomic-site iron on N-doped carbon(Fe_(SA)@NC-20A)via the pyrolysis of aniline modified FeZn-ZIFs,in which the synthesis of zeolitic imidazolate frameworks(ZIFs)can be accomplished in water at room temperature,and no acid etching is required.The as-synthesized catalyst exhibits better performance on the chemoselective hydrogenation of nitroarenes with a broad substrate scope(turnover frequency(TOF)up to 1,727 h^(-1),23 examples)than most of previously reported works.Based on high-angle annular dark field scanning transmission microscopy(HAADF-STEM)images in combination with X-ray photoelectron spectroscopy(XPS),X-ray absorption spectroscopy(XAS),electron spin resonance(ESR),and Mossbauer spectroscopy,Fe is dispersed as single atoms via forming FeNx(x=4-6).This work not only determines the active sites of FesA@NC-20A for hydrogenation(FeN4),but also proposes tentative pathways for both N-H activation of hydrazine and the reduction of nitroarene on FeN4 site,both of which are the key steps for the hydrogenation of nitroarenes.In addition,this catalyst shows excellent stability,and no significant activity degradation is observed when recycling for 10 times or restoring in air for 2 months.
基金supported by the National Natural Science Foundation of China(21473155,21273198)Natural Science Foundation of Zhejiang Province(LZ12B03001)~~
文摘Iron catalysis has attracted a wealth of interdependent research for its abundance,low price,and nontoxicity.Herein,a convenient and stable iron oxide(Fe2O3)‐based catalyst,in which active Fe2O3nanoparticles(NPs)were embedded into carbon films,was prepared via the pyrolysis of iron‐polyaniline complexes on carbon particles.The obtained catalyst shows a large surface area,uniform pore channel distribution,with the Fe2O3NPs homogeneously dispersed across the hybrid material.Scanning electron microscopy,Raman spectroscopy and X‐ray diffraction analyses of the catalyst prepared at900°C(Fe2O3@G‐C‐900)and an acid‐pretreated commercial activated carbon confirmed that additional carbon materials formed on the pristine carbon particles.Observation of high‐resolution transmission electron microscopy images also revealed that the Fe2O3NPs in the hybrid were encapsulated by a thin carbon film.The Fe2O3@G‐C‐900composite was highly active and stable for the direct selective hydrogenation of nitroarenes to anilines under mild conditions,where previously noble metals were required.The synthetic strategy and the structure of the iron oxide‐based composite may lead to the advancement of cost‐effective and sustainable industrial processes.
基金supported by the National Natural Science Foundation of China(21422308,21403216,21273231)Dalian Excellent Youth Foundation(2014J11JH126)~~
文摘We present an efficient approach for the chemoselective synthesis of arylamines from nitroarenes and formate over an oxygen-implanted MoS2 catalyst（O-MoS2）.O-MoS2 was prepared by incomplete sul idation and reduction of an ammonium molybdate precursor.A number of Mo-O bonds were implanted in the as-synthesized ultrathin O-MoS2 nanosheets.As a consequence of the different coordination geometries of O（Mo O2） and S（MoS2）,and lengths of the Mo-O and Mo-S bonds,the implanted Mo-O bonds induced obvious defects and more coordinatively unsaturated（CUS） Mo sites in O-MoS2,as confirmed by X-ray diffraction,Raman spectroscopy,X-ray photoelectron spectroscopy,high resolution transmission electron microscopy,and extended X-ray absorption fine structure characterization of various MoS2-based materials.O-MoS2 with abundant CUS Mo sites was found to efficiently catalyze the chemoselective reduction of nitroarenes to arylamines.
基金This work is supported by the National Natural Science Foundation of China(91634201,21403192 and 91645105)the China Postdoctoral Science Foundation(2018M630662)。
文摘Product selectivity adjustment is a much-studied topic in mesoscience that is critical for industrial processes and strongly related to reaction intermediates formed by interactions between catalytic active sites and reactants.Herein,we report efficient adjustment of the product selectivity in the hydrogenation of substituted nitroarenes via rational reaction intermediates achieved using controllable Pd nanoparticles.Pd nanoparticles fixed within zeolite Beta crystals(Pd@Beta)afforded rational Pd-NO2 interactions,in which the Pd nanoparticle-adsorbed substituted nitroarenes,such as nitrobenzaldehyde,were reasonably hydrogenated into the corresponding aminobenzaldehyde.However,for Pd nanoparticles supported on the external surfaces of zeolite beta crystals,various side products were obtained owing to the coexistence of Pd-NO2 and Pd-C=O interactions.When Pd nanoparticles were artificially controlled in various positions in a fixed-bed reactor,the product selectivity was significantly affected.These results demonstrate the importance of molecular adsorption and diffusion processes in adjusting product selectivity in catalytic reactions.
文摘In this study we designed a novel,cost‐efficient and green method for the synthesis of copper nanoparticles(Cu NPs)supported on manganese dioxide(MnO2)NPs,using Centella asiatica L.leaf extract as a naturally‐sourced reducing agent,without stabilizers or surfactants.This synthetic process is environmentally‐friendly and avoids the use of toxic reducing agents.Phenolic hydroxyl groups in the leaf extract are believed to reduce Cu2+in solution to generate Cu NPs that are subsequently stabilized on the MnO2NP surfaces.The resulting Cu/MnO2nanocomposite was fully characterized using X‐ray diffraction,transmission electron microscopy,field emission scanning electron microscopy,energy‐dispersive X‐ray spectroscopy and Fourier transform infrared spectroscopy.This material was found to function as a highly active,efficient and recyclable heterogeneous catalyst for the reduction of Congo red,rhodamine B and methylene blue as well as nitro compounds such as2,4‐dinitrophenylhydrazine and4‐nitrophenol in the presence of NaBH4in aqueous media at ambient temperature.The high stability of the Cu/MnO2nanocomposite also allows the catalyst to be separated and reused several times without any significant loss of activity.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金supported by the USTC Research Funds of the Double First-Class Initiative(YD3530002002)the Fundamental Research Funds for the Central Universities(WK2060000043 and WK3530000013)the National Science Foundation of Anhui Province(2208085J26 and 2208085QB36).
