The selective hydrogenation of phenol to cyclohexanone is an important process in the chemical industry.However,achieving high selectivity at high conversion rates is highly challenging,particularly under continuous r...The selective hydrogenation of phenol to cyclohexanone is an important process in the chemical industry.However,achieving high selectivity at high conversion rates is highly challenging,particularly under continuous reaction conditions.Here,we found that the presence of Na alkaline additives(NaX,X=CO3^2–,HCO^3–,or OH^–)on Pd/Al2O3 not only promoted the phenol conversion from 8.3%to>99%but also increased the cyclohexanone selectivity from 89%to>97%during the continuous hydrogenation of phenol on a fixed bed reactor.After 1200 h of continuous reaction,no activity or selectivity attenuation was observed and the turnover number was approximately 2.9×10^5.Density functional theory calculations,spectroscopic,and dynamics studies demonstrated that the addition of NaX greatly promoted phenol adsorption and hydrogen activation,thereby improving catalytic activity.Simultaneously,the formation of a“-C=O-Na-”intermediate inhibited the excessive hydrogenation and intermolecular coupling of cyclohexanone,leading to high selectivity.展开更多
Cyclohexanol is an important intermediate in the synthesis of Nylon-6 and plasticizers. In this work,cobalt oxide nanoparticles（NPs） supported on porous carbon（Co Ox@CN） were fabricated by one-pot method and the h...Cyclohexanol is an important intermediate in the synthesis of Nylon-6 and plasticizers. In this work,cobalt oxide nanoparticles（NPs） supported on porous carbon（Co Ox@CN） were fabricated by one-pot method and the hybrids could efficiently and selectively hydrogenate phenol to cyclohexanol with a high yield of 98%. The high catalytic performance of Co Ox@CN was associate with the high surface area（340 m2/g） and uniformly dispersed NPs. Furthurmore, by detailed analysing the relationship between catalytic activity and catalysts composition, it clearly indicated that the Co3O4 in Co Ox@CN played an important role for the adsorption and activation of phenol and the in situ gernerated Co was responsible for hydrogen adsorption and dissociation. These findings provide a fundamental insight into the real active sites in hydrogenation of phenol using Co-based catalysts.展开更多
Hydrogenation of lignin-derived phenol to KA oil(the mixture of cyclohexanone(K)and cyclohexanol(A))is attractive yet challenging in the sustainable upgrading of biomass derivatives under mild conditions.Traditional s...Hydrogenation of lignin-derived phenol to KA oil(the mixture of cyclohexanone(K)and cyclohexanol(A))is attractive yet challenging in the sustainable upgrading of biomass derivatives under mild conditions.Traditional supported metal catalysts have been widely studied but the active components on supports often exhibit low recyclability due to their instability under experimental conditions.Here we show fabricating ultrasmall Pt/NiO in the pores of chromium terephthalate MIL-101 as catalysts for hydrogenation of phenol.Impressively,Pt/NiO@MIL-101 achieves catalytic phenol hydrogenation to KA oils of tunable K/A ratios and good reusability under room temperature and atmospheric hydrogen pressure,superior to contrast Pt@MIL-101 and Pt/NiO samples.Such excellent performance mainly originates from the effective adsorption and activation of phenol by coordinatively unsaturated Cr sites and H2 activation on ultrasmall Pt/NiO as well as its effective spillover to the adsorbed phenol over Cr sites for hydrogenation reaction.Substantially,such catalyst also displays the excellent performances for hydrogenation of phenol’s derivatives under mild conditions.展开更多
Alumina(Al_(2)O_(3))is widely used in the chemical industry as the catalyst and support due to its high specific surface area,abundant pore size distribution and chemical stability.However,the occurrence of hydration ...Alumina(Al_(2)O_(3))is widely used in the chemical industry as the catalyst and support due to its high specific surface area,abundant pore size distribution and chemical stability.However,the occurrence of hydration in water environment,result in outstanding decrease in specific surface area and collapse of pore structure.In this work,dodecyl phosphoric acid(PA)is used to modify the surface of Al_(2)O_(3)to obtain a series of hydrophobic material(Al_(2)O_(3)-PA).Based on XPS and NMR analysis,PA is chemically bonded on Al_(2)O_(3)to form PAOAAl bond.Furthermore,BET and WCA results display that Al_(2)O_(3)-1PA exhibits excellent the hydrophobicity and hydrothermal stability while maintains the pore structure.Take it as the substrate to support the Pd nanoparticles,the as-prepared Pd/Al_(2)O_(3)-PA shows the superior catalytic performance in the hydrogenation of phenol and anthraquinone relative to Pd/Al_(2)O_(3),indicating the accessibility of Pd sites after PA modification.Especially,the significantly enhanced stability is also obtained in four cycles for aqueous phenol hydrogenation.This can be ascribed that the PA modification inhibits the aggregation of Pd nanoparticles and the products adhesion in the reaction process.The extension of PA coatings to monolithic catalysts could expand their current capabilities in industrial applications and warrants ongoing investigation.展开更多
基金supported by the National Natural Science Foundation of China (21622308)Key Program Supported by the Natural Science Foundation of Zhejiang Province, China (LZ18B060002)the Fundamental Research Funds for the Central Universities (2017XZZX002-16)~~
文摘The selective hydrogenation of phenol to cyclohexanone is an important process in the chemical industry.However,achieving high selectivity at high conversion rates is highly challenging,particularly under continuous reaction conditions.Here,we found that the presence of Na alkaline additives(NaX,X=CO3^2–,HCO^3–,or OH^–)on Pd/Al2O3 not only promoted the phenol conversion from 8.3%to>99%but also increased the cyclohexanone selectivity from 89%to>97%during the continuous hydrogenation of phenol on a fixed bed reactor.After 1200 h of continuous reaction,no activity or selectivity attenuation was observed and the turnover number was approximately 2.9×10^5.Density functional theory calculations,spectroscopic,and dynamics studies demonstrated that the addition of NaX greatly promoted phenol adsorption and hydrogen activation,thereby improving catalytic activity.Simultaneously,the formation of a“-C=O-Na-”intermediate inhibited the excessive hydrogenation and intermolecular coupling of cyclohexanone,leading to high selectivity.
基金Financial support from the key program supported by the Natural Science Foundation of Zhejiang Province, China (No. LZ18B060002)the National Natural Science Foundation of China (No. 21622308)+2 种基金the Specialized Research Fund for the Doctoral Program of Higher Education (No. J20130060)the Fundamental Research Funds for the Central Universitiesthe Program for Zhejiang Leading Team of S&T Innovation are greatly appreciated
文摘Cyclohexanol is an important intermediate in the synthesis of Nylon-6 and plasticizers. In this work,cobalt oxide nanoparticles（NPs） supported on porous carbon（Co Ox@CN） were fabricated by one-pot method and the hybrids could efficiently and selectively hydrogenate phenol to cyclohexanol with a high yield of 98%. The high catalytic performance of Co Ox@CN was associate with the high surface area（340 m2/g） and uniformly dispersed NPs. Furthurmore, by detailed analysing the relationship between catalytic activity and catalysts composition, it clearly indicated that the Co3O4 in Co Ox@CN played an important role for the adsorption and activation of phenol and the in situ gernerated Co was responsible for hydrogen adsorption and dissociation. These findings provide a fundamental insight into the real active sites in hydrogenation of phenol using Co-based catalysts.
基金the National Key Research and Development Program of China(No.2021YFA1500403)Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)+1 种基金the National Natural Science Foundation of China(Nos.52372079,22173024,and 21722102)Youth Innovation Promotion Association CAS(G.D.L.).
文摘Hydrogenation of lignin-derived phenol to KA oil(the mixture of cyclohexanone(K)and cyclohexanol(A))is attractive yet challenging in the sustainable upgrading of biomass derivatives under mild conditions.Traditional supported metal catalysts have been widely studied but the active components on supports often exhibit low recyclability due to their instability under experimental conditions.Here we show fabricating ultrasmall Pt/NiO in the pores of chromium terephthalate MIL-101 as catalysts for hydrogenation of phenol.Impressively,Pt/NiO@MIL-101 achieves catalytic phenol hydrogenation to KA oils of tunable K/A ratios and good reusability under room temperature and atmospheric hydrogen pressure,superior to contrast Pt@MIL-101 and Pt/NiO samples.Such excellent performance mainly originates from the effective adsorption and activation of phenol by coordinatively unsaturated Cr sites and H2 activation on ultrasmall Pt/NiO as well as its effective spillover to the adsorbed phenol over Cr sites for hydrogenation reaction.Substantially,such catalyst also displays the excellent performances for hydrogenation of phenol’s derivatives under mild conditions.
基金supported by National Key Research&Development Program of China(2021YFB3801600)Fundamental Research Funds for the Central University(buctrc201921,JD2223,12060093063)Innovative Achievement Commercialization Service-Platform of Industrial Catalysis(2019-00900-2-1).
文摘Alumina(Al_(2)O_(3))is widely used in the chemical industry as the catalyst and support due to its high specific surface area,abundant pore size distribution and chemical stability.However,the occurrence of hydration in water environment,result in outstanding decrease in specific surface area and collapse of pore structure.In this work,dodecyl phosphoric acid(PA)is used to modify the surface of Al_(2)O_(3)to obtain a series of hydrophobic material(Al_(2)O_(3)-PA).Based on XPS and NMR analysis,PA is chemically bonded on Al_(2)O_(3)to form PAOAAl bond.Furthermore,BET and WCA results display that Al_(2)O_(3)-1PA exhibits excellent the hydrophobicity and hydrothermal stability while maintains the pore structure.Take it as the substrate to support the Pd nanoparticles,the as-prepared Pd/Al_(2)O_(3)-PA shows the superior catalytic performance in the hydrogenation of phenol and anthraquinone relative to Pd/Al_(2)O_(3),indicating the accessibility of Pd sites after PA modification.Especially,the significantly enhanced stability is also obtained in four cycles for aqueous phenol hydrogenation.This can be ascribed that the PA modification inhibits the aggregation of Pd nanoparticles and the products adhesion in the reaction process.The extension of PA coatings to monolithic catalysts could expand their current capabilities in industrial applications and warrants ongoing investigation.
