The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfura...The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfural(HMF)to the gasoline additive2,5‐dimethylfuran(DMF),isespecially attractive.In this study,bimetallic Cu‐Co catalysts supported on CeO2,ZrO2,and Al2O3were used for the selective hydrogenolysis of HMF to DMF.The structures of the fresh and usedcatalysts were studied using X‐ray diffraction,the Brunauer‐Emmett‐Teller method,transmissionelectron microscopy,temperature‐programmed reduction by H2,temperature‐programmed desorptionof NH3,and CHNS analysis.The structures were correlated with the catalytic activities.TheCu‐Co/CeO2catalyst produced mainly2,5‐bis(hydroxymethyl)furan via reduction of C=O bonds onlarge Cu particles.The Cu‐Co/Al2O3catalyst gave the best selectivity for DMF,as a result of a combinationof highly dispersed Cu,mixed copper–cobalt oxides,and suitable weak acidic sites.Cu‐Co/ZrO2had low selectivity for DMF and produced a combination of variousover‐hydrogenolysis products,including2,5‐dimethyltetrahydrofuran and5,5‐oxybis(methylene)‐bis(2‐methylfuran),because of the presence of strong acidic sites.The reaction pathways and effectsof various operating parameters,namely temperature,H2pressure,and time,were studied to enableoptimization of the selective conversion of HMF to DMF over the Cu‐Co/Al2O3catalyst.展开更多
新疆塔木—卡兰古铅锌铜成矿带位于西昆仑与塔里木盆地的结合带 ,是近年来新发现的一个大型矿带。通过对含矿岩系的岩石化学、成矿元素、硫同位素、稀土元素的研究 ,并结合流体包裹体成分及H、O同位素的综合研究分析 ,认为该成矿带可分...新疆塔木—卡兰古铅锌铜成矿带位于西昆仑与塔里木盆地的结合带 ,是近年来新发现的一个大型矿带。通过对含矿岩系的岩石化学、成矿元素、硫同位素、稀土元素的研究 ,并结合流体包裹体成分及H、O同位素的综合研究分析 ,认为该成矿带可分为两种矿床类型 ,即砂砾岩型铅铜 (钴 )矿和碳酸盐岩型铅锌矿。二者为同一热卤水成矿系统的不同成矿阶段的产物 ,两类矿床可互为找矿标志。下部砂砾岩型矿床的成矿元素组合为Cu Co Pb Ag As(Ni Zn Cd) ,硫同位素组成表明富集轻硫 ,海底热液活动不强烈 ;上部碳酸盐岩型矿床的成矿元素组合为Pb Zn Cd As Ag Ba ,硫同位素分布具塔式结构 ,显示具海水还原硫和深源硫的混合来源 ,有强烈的海底热液活动。提出该成矿带的找矿目标应以上部碳酸盐岩型铅锌矿为主 ,同时应当注意下部砂砾岩型铅铜矿及其含铜砂页岩中钴的综合评价和工业利用。展开更多
Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structur...Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structures prepared by a one‐step citrate complexing method.The catalytic performances of the Cu‐LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions.The catalyst with 10 wt%Cu loading exhibited the best catalytic performance after prereduction in 5%H2‐95%N2,achieving a high FFA conversion of 100%and selectivity of 55.5%for 1,5‐pentanediol(40.3%)and 1,2‐pentanediol(15.2%)at 413 K and 6 MPa H2.This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity.Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs,especially to 1,5‐PeD,while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol(THFA).Therefore,it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5‐/1,2‐pentanediol selectivity ratio during FFA hydrogenolysis.展开更多
The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be ...The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be short lived,and therefore expensive,and unsuitable for use in wastewater treatment.In this work,we developed a bimetallic CuO-Co3O4@γ-Al2O3 catalyst for phenol degradation with bicarbonate-activated H2O2.The weakly basic environment provided by the bicarbonate buffer greatly suppresses leaching of active Cu and Co metal ions from the catalyst.X-ray diffraction and X-ray photoelectron spectroscopy results showed interactions between Cu and Co ions in the CuO-Co3O4@γ-Al2O3 catalyst,and these improve the catalytic activity in phenol degradation.Mechanistic studies using different radical scavengers showed that superoxide and hydroxyl radicals both played significant roles in phenol degradation,whereas singlet oxygen was less important.展开更多
文摘The hydrogenolysis of carbon–oxygen bonds is an important model reaction in upgrading biomass‐derived furanic compounds to transportation fuels.One of these model reactions,namelyconversion of5‐hydroxymethylfurfural(HMF)to the gasoline additive2,5‐dimethylfuran(DMF),isespecially attractive.In this study,bimetallic Cu‐Co catalysts supported on CeO2,ZrO2,and Al2O3were used for the selective hydrogenolysis of HMF to DMF.The structures of the fresh and usedcatalysts were studied using X‐ray diffraction,the Brunauer‐Emmett‐Teller method,transmissionelectron microscopy,temperature‐programmed reduction by H2,temperature‐programmed desorptionof NH3,and CHNS analysis.The structures were correlated with the catalytic activities.TheCu‐Co/CeO2catalyst produced mainly2,5‐bis(hydroxymethyl)furan via reduction of C=O bonds onlarge Cu particles.The Cu‐Co/Al2O3catalyst gave the best selectivity for DMF,as a result of a combinationof highly dispersed Cu,mixed copper–cobalt oxides,and suitable weak acidic sites.Cu‐Co/ZrO2had low selectivity for DMF and produced a combination of variousover‐hydrogenolysis products,including2,5‐dimethyltetrahydrofuran and5,5‐oxybis(methylene)‐bis(2‐methylfuran),because of the presence of strong acidic sites.The reaction pathways and effectsof various operating parameters,namely temperature,H2pressure,and time,were studied to enableoptimization of the selective conversion of HMF to DMF over the Cu‐Co/Al2O3catalyst.
文摘新疆塔木—卡兰古铅锌铜成矿带位于西昆仑与塔里木盆地的结合带 ,是近年来新发现的一个大型矿带。通过对含矿岩系的岩石化学、成矿元素、硫同位素、稀土元素的研究 ,并结合流体包裹体成分及H、O同位素的综合研究分析 ,认为该成矿带可分为两种矿床类型 ,即砂砾岩型铅铜 (钴 )矿和碳酸盐岩型铅锌矿。二者为同一热卤水成矿系统的不同成矿阶段的产物 ,两类矿床可互为找矿标志。下部砂砾岩型矿床的成矿元素组合为Cu Co Pb Ag As(Ni Zn Cd) ,硫同位素组成表明富集轻硫 ,海底热液活动不强烈 ;上部碳酸盐岩型矿床的成矿元素组合为Pb Zn Cd As Ag Ba ,硫同位素分布具塔式结构 ,显示具海水还原硫和深源硫的混合来源 ,有强烈的海底热液活动。提出该成矿带的找矿目标应以上部碳酸盐岩型铅锌矿为主 ,同时应当注意下部砂砾岩型铅铜矿及其含铜砂页岩中钴的综合评价和工业利用。
文摘Selective hydrogenolysis of biomass‐derived furfuryl alcohol(FFA)to 1,5‐and 1,2‐pentanediol(PeD)was conducted over Cu‐LaCoO3 catalysts with different Cu loadings;the catalysts were derived from perovskite structures prepared by a one‐step citrate complexing method.The catalytic performances of the Cu‐LaCoO3 catalysts were found to depend on the Cu loading and pretreatment conditions.The catalyst with 10 wt%Cu loading exhibited the best catalytic performance after prereduction in 5%H2‐95%N2,achieving a high FFA conversion of 100%and selectivity of 55.5%for 1,5‐pentanediol(40.3%)and 1,2‐pentanediol(15.2%)at 413 K and 6 MPa H2.This catalyst could be reused four times without a loss of FFA conversion but it resulted in a slight decrease in pentanediol selectivity.Correlation between the structural changes in the catalysts at different states and the simultaneous variation in the catalytic performance revealed that cooperative catalysis between Cu0 and CoO promoted the hydrogenolysis of FFA to PeDs,especially to 1,5‐PeD,while Co0 promoted the hydrogenation of FFA to tetrahydrofurfuryl alcohol(THFA).Therefore,it is suggested that a synergetic effect between balanced Cu0 and CoO sites plays a critical role in achieving a high yield of PeDs with a high 1,5‐/1,2‐pentanediol selectivity ratio during FFA hydrogenolysis.
基金supported by the National Natural Science Foundation of China(21273086)Chutian Scholar Foundation from Hubei Province,China~~
文摘The development of new catalytic techniques for wastewater treatment has long attracted much attention from industrial and academic communities.However,because of catalyst leaching during degradation,catalysts can be short lived,and therefore expensive,and unsuitable for use in wastewater treatment.In this work,we developed a bimetallic CuO-Co3O4@γ-Al2O3 catalyst for phenol degradation with bicarbonate-activated H2O2.The weakly basic environment provided by the bicarbonate buffer greatly suppresses leaching of active Cu and Co metal ions from the catalyst.X-ray diffraction and X-ray photoelectron spectroscopy results showed interactions between Cu and Co ions in the CuO-Co3O4@γ-Al2O3 catalyst,and these improve the catalytic activity in phenol degradation.Mechanistic studies using different radical scavengers showed that superoxide and hydroxyl radicals both played significant roles in phenol degradation,whereas singlet oxygen was less important.
