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1纤维素催化转化为高附加值化学品的研究进展(英文)显示文摘Currently,under huge pressure from energy demands and environmental problems,much attention is being paid to biomass conversion,which will play an important role in meeting the requirements for a sustainable society.As the most abundant biomass on earth, cellulose is usually used as the first research target for biomass conversion.In this review,the recalcitrant structure of cellulose is discussed and non-catalytic hydrolysis by hot-compressed water and catalytic hydrolysis using solid acids are then considered.We also review the catalytic conversion of cellulose into valuable chemicals including hexitols(sorbitol and mannitol),ethylene glycol,and related compounds using various heterogeneous catalysts.Hirokazu KOBAYASHI Atsushi FUKUOKA 2011催化学报2011,32,5:13
2Kinetics of Hydrogen Absorption in Hydrogen Storage Alloy显示文摘Hydrogenation kinetics of MLNi3.8(Co,Mn,Al)1.2 and MLNi3.7(Co,Mn,Al)1.2Cu0.1 alloy in α + β phase at the temperatUre range of 30 ~70 ℃ has been studied. The kinetic mechanism of hydrogen absorption is not affected by initial hydrogen pressure. Temperature does not influence the rate of hydrogen absorption obviously. In the prior and later period of hydrogen absorption the rate-controlling step is chemical reaction and hydrogen diffusion in the hydride phase respectively for MLNi3.8(Co,Mn,Al)1.2 alloy. Adding Cu, the rate-controlling step changes from chemical reaction to the nucleation and growth of β phase in the prior period and the process of hydrogen absorption still controlled by diffusion in the later period.LIN Qin CHEN Ning YE Wen LIU Renmin(Applied Science School, USTB, Beijing 100083, China) (General Research Institute of Non-Ferrous Metals Beijing, 100088) 1997International Journal of Minerals,Metallurgy and Materials1997,11,2:10
3Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil显示文摘A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.Minghao Zhou Zuo Zeng Hongyan Zhu Guomin Xiao Rui Xiao 2014Journal of Energy Chemistry2014,23,1:9
4Methanation of carbon dioxide:an overview显示文摘Although being very challenging,utilization of carbon dioxide(CO_(2))originating from production processes and flue gases of CO_(2)-intensive sectors has a great environmental and industrial potential due to improving the resource efficiency of industry as well as by contributing to the reduction of CO_(2) emissions.As a renewable and environmentally friendly source of carbon,catalytic approaches for CO_(2) fixation in the synthesis of chemicals offer the way to mitigate the increasing CO_(2) buildup.Among the catalytic reactions,methanation of CO_(2) is a particularly promising technique for producing energy carrier or chemical.This article focuses on recent developments in catalytic materials,novel reactors,and reaction mechanism for methanation of CO_(2).Wei WANG Jinlong GONG 2011Frontiers of Chemical Science and Engineering2011,5,1:9
5Synthesis of bifunctional Pt/MgAPO-5 catalysts and their catalytic performance in the hydrogenation of nitrobenzene to p-aminophenol显示文摘MgAPO-5 molecular sieves have been synthesized using diethylaminoethanol as the templating agent in a wide range of the MgO/Al2O3 ratio.The samples were characterized by XRD,SEM,solid state NMR,FT-IR and NH3-TPD.Using MgAPO-5 as acidic supports,bifunctional Pt/MgAPO-5 catalysts were prepared for hydrogenation of nitrobenzene to p-aminophenol (PAP).The results showed that the MgO/Al2O3 ratios influenced the Mg content and the acidity of MgAPO-5 samples,thereby greatly affecting the catalytic performance of Pt/MgAPO-5 catalysts.The selectivity to PAP over Pt/MgAPO-5 was dependent on the amount of strong acid sites of MgAPO-5.When the MgO/Al2O3 molar ratio was 0.5,the synthesized MgAPO-5 sample exhibited the largest amount of strong acid and a highest PAP yield of 41.1% was achieved over Pt/MgAPO-5 catalyst.ShuFang Wang YaDan Jin BeiBei He YanJi Wang XinQiang Zhao 2010Science China Chemistry2010,53,7:9
6Single Pt atom decorated graphitic carbon nitride as an efficient photocatalyst for the hydrogenation of nitrobenzene into aniline显示文摘The hydrogenation of nitrobenzene into aniline is one of industrially important reactions, but still remains great challenge due to the lack of highly active, chemo-selective and eco-friendly catalyst. By using extensive density functional theory (DFT) calculations, herein we predict that single Pt atom decorated g-C3N4 (Pt@g-C3N4) exhibits excellent catalytic activity and selectivity for the conversion of nitrobenzene into aniline under visible light. The overall activation energy barrier for the hydrogenation of nitrobenzene on single atom Pt@g-C3N4 catalyst is even lower than that of the bare Pt(111) surface. The dissociation of N-0 bonds on single Pt atom is triggered by single hydrogen atom rather than double hydrogen atoms on the Pt(111) surface. Moreover, the Pt@g-C3N4 catalyst exhibits outstanding chemoselectivity towards the common reducible substituents, such as phenyl,-C=C,-C = C and -CHO groups during the hydrogenation. In addition, the doped single Pt atom can significantly enhance the photoconversion efficiency by broadening the light absorption of the pristine g-C3N4 to visible light region. Our results highlight an interesting and experimentally synthesized single-atom photocatalyst (Pt@g-C3N4) for efficient hydrogenation of nitrobenzene to aniline under a sustainable and green approach.Tianwei He Chunmei Zhang Lei Zhang Aijun Du 2019Nano Research2019,12,8:8
7The scientific connotation of oil and gas formations under deep fluids and organic-inorganic interaction显示文摘As a relatively stable craton block in the earth system, the petroliferous basin is influenced by the evolution of the earth system from the early development environment of source rocks, hydrocarbon formation, and reservoir dissolution to hydrocarbon accumulation or destruction. As a link between the internal and external factors of the basin, deep fluids run through the whole process of hydrocarbon formation and accumulation through organic-inorganic interaction. The nutrients carried by deep fluids promote the bloom of hydrocarbon-generating organisms and extra addition of carbon and hydrogen source, which are beneficial to the development of high-quality source rock and enhancement of the hydrocarbon generation potential. The energy carried by the deep fluid promotes the early maturation of the source rock and facilitates the hydrocarbon generation by activation and hydrogenation in high-mature hydrocarbon sources. The dissolution alteration of carbonate rocks and clastic reservoirs by CO_2-rich deep fluids improves the deep reservoir space, thus extending the oil and gas reservoir space into greater depth. The extraction of deeply retained crude oil by deep supercritical CO_2 and the displacement of CH_4 in shale have both improved the hydrocarbon fluidity in deep and tight reservoirs. Simultaneously, the energy and material carried by deep fluids(C, H, and catalytic substances) not only induce inorganic CH_4 formation by Fischer-Tropsch(F-T) synthesis and 'hydrothermal petroleum' generation from organic matter by thermal activity but also cause the hydrothermal alteration of crude oil from organic sources. Therefore, from the perspective of the interaction of the earth's sphere, deep fluids not only input a significant amount of exogenous C and H into sedimentary basins but also improve the reservoir space for oil and gas, as well as their enrichment and accumulation efficiencies.Quanyou LIU Dongya ZHU Qingqiang MENG Jiayi LIU Xiaoqi WU Bing ZHOU Qi FU Zhijun JIN 2019Science China Earth Sciences2019,62,3:8
8A novel liquid system of catalytic hydrogenation显示文摘On the basis that endothermic aqueous-phase reforming of oxygenated hydrocarbons for H2 produc- tion and exothermic liquid phase hydrogenation of organic compounds are carried out under extremely close conditions of temperature and pressure over the same type of catalyst, a novel liquid system of catalytic hydrogenation has been proposed, in which hydrogen produced from aqueous-phase re- forming of oxygenated hydrocarbons is in situ used for liquid phase hydrogenation of organic com- pounds. The usage of active hydrogen generated from aqueous-phase reforming of oxygenated hy- drocarbons for liquid catalytic hydrogenation of organic compounds could lead to increasing the se- lectivity to H2 in the aqueous-phase reforming due to the prompt removal of hydrogen on the active centers of the catalyst. Meanwhile, this novel liquid system of catalytic hydrogenation might be a po- tential method to improve the selectivity to the desired product in liquid phase catalytic hydrogenation of organic compounds. On the other hand, for this novel liquid system of catalytic hydrogenation, some special facilities for H2 generation, storage and transportation in traditional liquid phase hydrogenation industry process are yet not needed. Thus, it would simplify the working process of liquid phase hy- drogenation and increase the energy usage and hydrogen productivity.LI XiaoNian XIANG YiZhi 2007Science China Chemistry2007,50,6:7
9Bimetallic Ru-Ni/TiO2 catalysts for hydrogenation of N-ethylcarbazole:Role of TiO2 crystal structure显示文摘Hydrogenation of N-ethylcarbazole(NEC),the hydrogen lean form of a liquid organic hydrogen carrier,on TiO2 supported Ru-Ni bimetallic catalysts is investigated.Crystal structure of TiO2 plays a critical role on the hydrogenation activity and selectivity towards fully hydrogenated product.Ru/anatase catalyst exhibits higher selectivity but lower reactivity compared to Ru/rutile catalyst.Ni addition significantly promotes the performance of Ru/anatase catalyst while causes severe performance deterioration of Ru/rutile catalyst.Commercial P25,a mixture of anatase and rutile phases in approximate ratio A/R1/4,is found to be the best TiO2 support for NEC hydrogenation.Ru/P25 catalyst outperforms both Ru/rutile and Ru/anatase and its activity can be further slightly improved by Ni addition.The unexpected synergism between the two different TiO2 phases for Ru based NEC hydrogenation catalysts is related to metal-support interaction and Ru-Ni interaction.Hongen Yu Xue Yang Yong Wu Yanru Guo Shuan Li Wei Lin Xingguo Li Jie Zheng 2020Journal of Energy Chemistry2020,29,1:7
10Catalytic carbon dioxide hydrogenation to methane: A review of recent studies显示文摘Recently,various efforts have been put forward on the development of technologies for the synthesis of methane from CO_2 and H_2,since it can offer a solution for renewable H_2 storage and transportation.In parallel,this reaction is considered to be a critical step in reclaiming oxygen within a closed cycle.Over the years,extensive fundamental research works on CO_2 methanation have been investigated and reported in the literatures.In this updated review,we present a comprehensive overview of recent publications during the last 3 years.Various aspects on this reaction system are described in detail,such as thermodynamic considerations,catalyst innovations,the influence of reaction conditions,overall catalytic performance,and reaction mechanism.Finally,the future development of CO_2 methanation is discussed.Xiong Su Jinghua Xu Binglian Liang Hongmin Duan Baolin Hou Yanqiang Huang 2016Journal of Energy Chemistry2016,25,4:7
11Structural elucidation of sex pheromone components of the Geometridae Semiothisa cinerearia(Bremer et Grey)in China显示文摘An extract from the female sex gland of Semiothisa cinerearia attracted conspecificmales in field tests.A major active component was isolated from the extract and identified byGC-MS,GC-IR and microchemical reactions as cis-3,4-cpoxy-(Z,Z)-6,9-heptadecadiene,whichshowed strong EAG response.Another minor yet important component was identified as(Z,Z,Z)-3,6,9-heptadecatriene.LI,Zheng-Ming YAO,En-Yun LIU,Tian-Lin LIU,Zi-Ping WANG,Su-Hua Elemento-Organic Chemistry Institute,Nankai University,Tianjin 300071ZHU,Hai-Qing ZHAO,Gang REN,Zi-Li Department of Biology,Nankai University,Tianjin 300071 1993Chinese Journal of Chemistry1993,11,3:6
12Selective hydrogenation of acetylene on SiO_2-supported Ni-Ga alloy and intermetallic compound显示文摘Ni/Si O_2 and bimetallic Ni_xGa/SiO_2 catalysts with different Ni/Ga atomic ratios(x = 10~2) were investigated for the selective hydrogenation of acetylene.It was found that Ni_xGa/SiO_2 showed higher selectivity to ethylene than Ni/Si O_2.This is attributed to the formation Ni-Ga alloy and Ni3 Ga intermetallic compound(IMC) where there was a charge transfer from Ga to Ni,which is favorable for reducing the adsorption strength and amount of ethylene on Ni atoms.As a result,the over-hydrogenation,the C–C bond hydrogenolysis and the polymerization were suppressed,and subsequently the selectivity to ethylene was enhanced.With the decrease of Ni/Ga atomic ratio,the activity and stability of the Ni_xGa/SiO_2 catalysts increased first and then decreased,while the ethylene selectivity tended to increase.Ni_5 Ga/SiO_2 exhibited the best performance.Under the conditions of 180 °C,0.1 MPa,and a reactant(1.0 vol% acetylene,5.0 vol% H_2 and 94 vol% N_2) with the space velocity of 36,000 m L h^(-1) g^(-1),the acetylene conversion maintained at 100% on Ni_5 Ga/SiO_2 during 120 h time on stream and the selectivity to ethylene was 75%~81%after reaction for 68 h.It was also found that the formation of Ni-Ga alloy and Ni_3 Ga IMC suppressed the incorporation of carbon to form NiCx,subsequently enhancing the catalyst stability.Additionally,with increasing the Ga content,the catalyst acid amount and strength tended to increase,which promoted the polymerization and carbon deposition and so the catalyst deactivation.Lei Wang Fengxu Li Yanjun Chen Jixiang Chen 2019Journal of Energy Chemistry2019,28,2:6
13TiO_2担载镍催化剂上硝基苯液相加氢(英文)显示文摘The catalytic hydrogenation of nitrobenzene to aniline employing nickel impregnated on rutile,anatase,and high surface area titania supports has been investigated.The nickel is present in elemental state as fcc phase on the catalyst as evidenced by X-ray diffraction results.The Ni crystallite size was found to be greater for Ni/anatase.The temperature-programmed reduction results suggest a greater metal-support interaction for Ni/rutile.The observed order of catalytic activity for the hydrogenation of nitrobenzene is Ni/rutile > Ni/anatase > Ni/TiO2.A conversion of 99% was observed for Ni/rutile at 140 oC and hydrogen pressure of 1.96 MPa.Interestingly,aniline is the only product formed which demonstrates the catalytic hydrogenation of nitrobenzene proceeds with atom economy.Both Ni/rutile and Ni/anatase exhibited a better stability than Ni/TiO2.The hydrogenation proceeds with the preferential adsorption of hydrogen on nickel present in the catalyst surface,possibly assisted by TiOx species.K.Joseph Antony RAJ M.G.PRAKASH R.MAHALAKSHMY T.ELANGOVAN B.VISWANATHAN 2012催化学报2012,33,8:6
14Fe5C2 nanoparticles as low-cost HER electrocatalyst:the importance of Co substitution显示文摘Constructing and understanding the doping effect of secondary metal in transition metal carbide(TMC)catalysts is pivotal for the design of low-cost hydrogen evolution reaction(HER) electrocatalysts. In this work, we developed a wet-chemistry strategy for synthesizing Co-modified Fe_5C_2 nanoparticles((Fe_(1-x)Cox)_5C_2 NPs) as highly active HER electrocatalysts in basic solution. The structure of(Fe_(1-x)Cox)_5C_2 NPs was characterized by X-ray diffraction(XRD), extended X-ray absorption fine structure spectra(EXAFS) and scanning/transmission electron microscopy(S/TEM), indicating that the isomorphous substitution of cobalt in the lattice of Fe_5C_2.(Fe_(0.75) Co_(0.25))_5C_2 exhibited the best HER activity(174 mV for j = -10 mA/cm^2). Computational calculation results indicate that Co provides the most active site for HER. X-ray adsorption spectra(XAS) studies further suggested that the electron transfer in Fe–C bonds are enhanced by the substitution of Co, which modulates the hydrogen adsorption on the adjacent electronic-enriched carbon, and therefore promotes HER activity. Our results affirm the design of lowcost bimetallic TMCs based HER catalysts.Siwei Li Pengju Ren Ce Yang Xi Liu Zhen Yin Weizhen Li Hanjun Yang Jian Li Xiaoping Wang Yi Wang Ruochen Cao Lili Lin Siyu Yao Xiaodong Wen Ding Ma 2018Science Bulletin2018,63,20:6
15Selective hydrogenation of N-heterocyclic compounds over rhodium-copper bimetallic nanocrystals under ambient conditions显示文摘Bimetallic nanocrystals (BMNCs) with distinguished electronic and chemical properties from those of their parent metals,offer the opportunity to obtain new catalysts with enhanced selectivity,activity,and stability.Here we describe the facile synthesis of rhodium-copper bimetallic system with different compositions and uniform morphology for chemo selective hydrogenation of functionalized quinolines.Our findings demonstrate that Rh-Cu BMNCs exhibited composition dependent activity and selectivity.BMNCs with rhodium to copper ratio 3:1 surpassed individual Rh and Cu and other compositions both in activity and selectivity for quinolines hydrogenation and performed even better than Rh/C with same amount of Rh.Rh3Cui catalyst displayed excellent tolerance for synthetically significant functional groups such as -OH,NH2,F,particularly for aldehyde group which is very reactive towards reduction.These results suggested that the coexistence of rhodium and copper metals play important role in the enhancement of catalytic activity due to synergistic effects and revealed that bimetallic nanocrystals can be promising as practical catalysts for selective hydrogenation of quinoline and other substrates.Muhammad Mateen Khadim Shah Zheng Chen Chen Chen Yadong Li 2019Nano Research2019,12,7:6
16SMFs-supported Pd nanocatalysts in selective acetylene hydrogenation:Pore structure-dependent deactivation mechanism显示文摘In the present study,CNFs,ZnO and Al2O3 were deposited on the SMFs panels to investigate the deactivation mechanism of Pd-based catalysts in selective acetylene hydrogenation reaction.The examined supports were characterized by SEM,NH3-TPD and N2adsorption-desorption isotherms to indicate their intrinsic characteristics.Furthermore,in order to understand the mechanism of deactivation,the resulted green oil was characterized using FTIR and SIM DIS.FTIR results confirmed the presence of more unsaturated constituents and then,more branched hydrocarbons formed upon the reaction over alumina-supported catalyst in comparison with the ones supported on CNFs and ZnO,which in turn,could block the pores mouths.Besides the limited hydrogen transfer,N2 adsorption-desorption isotherms results supported that the lowest pore diameters of Al2O3/SMFs close to the surface led to fast deactivation,compared with the other catalysts,especially at higher temperatures.Elaheh Esmaeili Ali Morad Rashidi Yadollah Mortazavi Abbas Ali Khodadadi Mehdi Rashidzadeh 2013Journal of Energy Chemistry2013,22,5:5
17Partial hydrogenation of adiponitrile to 6-aminocapronitrile over Ni/α-Al_2O_3 catalyst promoted with K_2O and La_2O_3显示文摘A novel K2O and La2O3 promoted nickel catalyst supported on a-Al2O3 was prepared by co-impregnation method, and it exhibited higher activity and 6-aminocapronitrile selectivity than Ni/a-Al2O3 during the hydrogenation of adiponitrile in the absence of ammonia, i.e., K2O and La2O3 improved the performance of the nickel-based catalyst.Lei Zhao, Cai Yun Wang, Ji Xiang Chen , Ji Yan Zhang Department of Catalysis Science and Engineering, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China 2007Chinese Chemical Letters2007,18,6:5
18Asymmetric Catalysis with Chiral Frustrated Lewis Pairs显示文摘The chemistry of frustrated Lewis pairs(FLPs)provides the most important approach for the metal-free hydrogenation and hydrosilylations.Great progress has been achieved in this area for the past decade.Some promising results have also been obtained.This perspective article mainly focuses on the recent advances for the synthesis of chiral Lewis acidic boranes in category of three protocols,1)hydroboration of chiral internal alkenes with Piers'borane HB(C6F5)2;2)in situ hydroboration of chiral alkenes or alkynes without any purification;3)and substitution reaction of(C6F5)nBCl3-n with chiral organometallic reagents,as well as their applications in the metal-free asymmetric hydrogenations and hydrosilylations.Wei Meng Xiangqing Feng Haifeng Du 2020Chinese Journal of Chemistry2020,38,6:5
19One-Step High-Temperature-Synthesized Single-Atom Platinum Catalyst for Efficient Selective Hydrogenation显示文摘Although single-atom catalysts significantly improve the atom utilization efficiency,the multistep preparation procedures are complicated and difficult to control.Herein,we demonstrate that one-step in situ synthesis of the single-atom Pt anchored in single-crystal MoC(Pt_(1)/MoC)by using facile and controllable arc-discharge strategy under extreme conditions.The high temperature(up to 4000℃)provides the sufficient energy for atom dispersion and overall stability by forming thermodynamically favourable metal-support interactions.The high-temperature-stabilized Pt1/MoC exhibits outstanding performance and excellent thermal stability as durable catalyst for selective quinoline hydrogenation.The initial turnover frequency of 3710 h^(-1)is greater than those of previously reported samples by an order of magnitude under 2 MPa H_(2)at 100℃.The catalyst also shows broad scope activity toward hydrogenation containing unsaturated groups of C=C,C=N,and C=O.The facile,one-step,and fast arc-discharge method provides an effective avenue for single-atom catalyst fabrication that is conventionally challenging.Qingyuan Bi Xiaotao Yuan Yue Lu Dong Wang Jian Huang Rui Si Manling Sui Fuqiang Huang 2020Research2020,,1:5
20Effect of Preparation Process on Compressive Strength and Hydrogenation Performance of Raney-Ni/Al2O3 Catalyst显示文摘In this study, Raney-Ni/Al_2O_3 catalysts were prepared from precursors which were calcined in different atmosphere(argon and air) and leached for different time. XRD, SEM, H_2-TPR and BET techniques were introduced to characterize the catalysts, and hydrogenation of unsaturated hydrocarbons, including vinyltoluene, dicyclopentadiene and indene, was used as probe reaction to evaluate the catalytic hydrogenation performance of the catalysts. The results demonstrated that the calcination atmosphere had noticeable effects on the compressive strength and hydrogenation performance of Raney-Ni/Al_2O_3. The catalyst calcined in argon exhibited better compressive strength and catalytic performance than the one calcined in air. The compressive strength and activity stability of catalyst were also determined by the leaching time. A too longer leaching time was not conducive to improving the compressive strength and catalytic performance of catalysts. When the precursor calcined in argon was treated in a 15%(by wt.) sodium hydroxide solution at 343 K for 5 h, a catalyst with higher compressive strength(at 26.10 N/mm) was obtained and the conversion of vinyltoluene, dicyclopentadiene(DCPD), and indene could amount to more than 87.5%, 99% and even 100%, respectively, under the reaction conditions covering a temperature of 493 K, a hydrogen pressure of 2.0 MPa, a LSHV of 3.0 h^(-1), and a hydrogen/oil ratio of 200:1.Luo Guohua Wang Yanli Sun Daming Xu Xin Jin Haibo 2017China Petroleum Processing & Petrochemical Technology2017,19,2:5
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