2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production o...2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural(HMF)and its derivatives is still rudimentary under base-free conditions.In this work,oxygen-vacancy-rich Mn Oxwas prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the(210)plane of RuO_(2),bringing about highly dispersed and active interfacial Ru-O-Mn structures.Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural(MMF),which enables an efficient FDCA production under base-free and mild conditions.Notably,a desirable FDCA yield of 86.56%was still obtained from concentrated HMF(10 wt%)under base-free conditions over oxygen-vacancy-rich Mn Oxsupported Ru Ox(1.0 MPaO_(2),120℃,6 h).This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation,and might open a new avenue for the green synthesis of FDCA under base-free conditions.展开更多
Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydr...Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.展开更多
Selective oxidation of glycerol with molecular oxygen in base-free aqueous solutions has become a hot topic,as the rapidly increasing production of biodiesel is creating a surplus of glycerol.In this work,an N-doped-c...Selective oxidation of glycerol with molecular oxygen in base-free aqueous solutions has become a hot topic,as the rapidly increasing production of biodiesel is creating a surplus of glycerol.In this work,an N-doped-carbon-supported core-shell structured Sb@PtSb2 hybrid catalyst was prepared via a facile synthesis route,in which a mixture of glucose,melamine,and SbCl3(Sb-NC)was pyrolyzed,then impregnated with Pt by immersion in an aqueous solution of H2PtCl6,and further treated in hydrogen flow.Characterization of the catalyst products indicated that introducing SbCl3 can increase the surface area of the binary glucose+melamine pyrolyzed support(NC),and Sb@PtSb2 hybrids could be formed on the surface of an Sb-NC support during hydrogen treatment at 700℃.It was found that the Sb@PtSb2/NC catalyst was more active for the selective oxidation of glycerol in a base-free aqueous solution than Sb-free NC-supported Pt(Pt/NC).Further characterization also indicated that the promising performance of Sb@PtSb2/NC might be attributed to its enhanced oxygen activation.展开更多
Understanding the nature of Pt active sites is of great importance for the structure-sensitive base-free oxidation of glycerol. In the present work, the remarkable Pt particle size effects on glycerol conversion and p...Understanding the nature of Pt active sites is of great importance for the structure-sensitive base-free oxidation of glycerol. In the present work, the remarkable Pt particle size effects on glycerol conversion and products formation from the oxidation of the primary and the secondary hydroxyl groups are understood by combining the model calculations and DFT calculations, aiming to discriminate the corresponding dominant Pt active sites. The Pt(100) facet is demonstrated to be the dominant active sites for the glycerol conversion and the products formation from the two routes. The insights revealed here could shed new light on fundamental understanding of the Pt particle size effects and then guiding the design and optimization of Pt-catalyzed base-free oxidation of glycerol toward targeted products.展开更多
The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold...The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold catalysts showed much better catalytic activity for base-free aerobic oxidation of benzyl alcohol than Au/ZnO and Au/CuO catalysts,and among them Au/Zn0.7Cu0.3O displayed the best catalytic performance.In addition,the Au/Zn0.7Cu0.3O catalyst could selectively catalyze the aerobic oxidation of a wide range of alcohols to produce the corresponding carbonyl compounds with high yields under mild conditions without base.Further characterizations indicated that the outstanding catalytic performance of Au/Zn0.7Cu0.3O was correlated with the small size of Au nanoparticles(NPs),good low-temperature reducibility,high concentration of surface oxygen species,and collaborative interaction between Au NPs and mixed oxide.展开更多
An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources ...An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources such as methanol are not needed in this catalytic system. This reaction could be performed successfully under ligand- and base-free conditions. It demonstrated that phenylpropiolic acids can be employed as alkyne synthons in the hydroboration reaction and exhibited good reactivity and higher selectivity than terminal alkynes.展开更多
A base-free catalyst system Co(acac)3/BMMImCl was developed for the carbonylation of amines with CO2.45%-81% isolated yields for N,N'-dialkylureas and 6%-23% isolated yields for N,N-diarylureas were obtained.The c...A base-free catalyst system Co(acac)3/BMMImCl was developed for the carbonylation of amines with CO2.45%-81% isolated yields for N,N'-dialkylureas and 6%-23% isolated yields for N,N-diarylureas were obtained.The catalyst system was recovered and reused without significant loss in activity.In this catalyst system,the base catalyst and chemical dehydrant were efficiently avoided.Different reaction conditions were also discussed and a postulated mechanism was proposed.展开更多
Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(A...Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(Au/CNT-O and Au/CNT-N)catalyst for base-free oxidation of monosaccharide into sugar acid.Au/CNT-O and Au/CNT-N surfaces successfully introduced oxygen-and nitrogen-containing functional groups,respectively.The highest yields of gluconic acid and xylonic acid were 93.3%and 94.3%,respectively,using Au/CNT-N at 90℃ for 240 min,which is higher than that of using Au/CNT-O.The rate constants for monosaccharide decomposition and sugar acid formation in Au/CNT-N system were higher,while the corresponding activation energy was lower than in Au/CNT-O system.DFT calculation revealed that the mechanism of glucose oxidation to gluconic acid involves the adsorption and activation of O_(2),adsorption of glucose,dissociation of the formyl C-H bond and formation of O-H bond,and formation and desorption of gluconic acid.The activation energy barrier for the glucose oxidation over Au/CNT-N is lower than that of Au/CNT-O.The nitrogen-containing functional groups are more beneficial for accelerating monosaccharide oxidation and enhancing sugar acid selectivity than oxygen-containing functional groups.This work presents a useful guidance for designing and developing highly active catalysts for producing high-value-added chemicals from biomass.展开更多
A base-free catalytic system for the aerobic oxidation of 5-hydroxymethyl-2-furfural was exploited by using Pt nanoparticles immobilized onto a thermoresponsive poly(acrylamide-co-acrylonitrile)-b-poly(N-vinylimidazol...A base-free catalytic system for the aerobic oxidation of 5-hydroxymethyl-2-furfural was exploited by using Pt nanoparticles immobilized onto a thermoresponsive poly(acrylamide-co-acrylonitrile)-b-poly(N-vinylimidazole)block copolymer,with an upper critical solution temperature of about 45°C.The Pt nanocatalysts were well-dispersed and highly active for the base-free oxidation of 5-hydroxymethyl-2-furfural by molecular oxygen in water,affording high yields of 2,5-furandicarboxylic acid(up to>99.9%).The imidazole groups in the block copolymer were conducive to the improvement of catalytic performance.Moreover,the catalysts could be easily separated and recovered based on their thermosensitivity by cooling the reaction system below the upper critical solution temperature.Good stability and reusability were observed over these copolymer-immobilized catalysts with no obvious decrease in catalytic activity in the five consecutive cycles.展开更多
CeO_(2) morphology was proposed to be a crucial factor for reducing nitrobenzene to azoxybenzene under the base-free condition.Herein,the structure-activity relationship of CeO_(2) catalysts was explored to improve th...CeO_(2) morphology was proposed to be a crucial factor for reducing nitrobenzene to azoxybenzene under the base-free condition.Herein,the structure-activity relationship of CeO_(2) catalysts was explored to improve the azoxybenzene yield.A series of CeO_(2) catalysts we re synthesized with seven morphologies to obtain different Ce^(3+) proportion and various surface areas.Notably,the catalytic performance of these samples for reducing nitrobenzene to azoxybenzene enhanced with the increasing Ce^(3+) proportio n.With the highest surface Ce^(3+) proportion,the Rod-CeO_(2) catalyst exhibited 100% conversion of nitrobenzene and 89.8% azoxybenzene selectivity in 7 h at 150℃ under 1 MPa CO.Moreover,the preliminary mechanistic analysis indicated that the inhabitation of azoxybenzene to by-product azobenzene resulted in the high selectivity of azoxybenzene.展开更多
基金the funding supported by the National Natural Science Foundation of China(22378338,22078275)the Natural Science Foundation of Fujian Province of China(2021H0009)the Fundamental Research Funds for the Central Universities(20720220065)。
文摘2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural(HMF)and its derivatives is still rudimentary under base-free conditions.In this work,oxygen-vacancy-rich Mn Oxwas prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the(210)plane of RuO_(2),bringing about highly dispersed and active interfacial Ru-O-Mn structures.Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural(MMF),which enables an efficient FDCA production under base-free and mild conditions.Notably,a desirable FDCA yield of 86.56%was still obtained from concentrated HMF(10 wt%)under base-free conditions over oxygen-vacancy-rich Mn Oxsupported Ru Ox(1.0 MPaO_(2),120℃,6 h).This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation,and might open a new avenue for the green synthesis of FDCA under base-free conditions.
基金supported by the National Natural Science Foundation of China(21773208,21473155)the Natural Science Foundation of Zhejiang Province(L12B03001)~~
文摘Catalytic transformation of glycerol to value-added products has attracted the attention of scientists all over the world. Among various transformations, selective oxidation of glycerol with molecular oxygen to dihydroxyacetone, glyceric acid, glyceraldehydes, and tartronic acid is challenging both from the viewpoint of academic research and industrial application. Herein, we review the recent progresses in the selective oxidation of glycerol under base-free conditions. Those catalysts widely reported for the selective oxidation of the terminal hydroxyl and secondary hydroxyl groups in glycerol, such as monometallic Au, Pt, and Pd NPs, and bimetallic Au-Pt, Au-Pd, Pt-Bi, Pt-Sb, and Pt-Cu, were compared and discussed in detail. The reaction mechanism over Pt-based catalysts, possible catalyst deactivation, and the corresponding improvements are presented. Further, the recent progresses in the continuous oxidation of glycerol in fixed bed reactors and its excellent selectivity in the formation of dihydroxyacetone are highlighted.
基金financially supported by the National Natural Science Foundation of China(21773206 and 21473155)Natural Science Foundation of Zhejiang Province(L12B03001)~~
文摘Selective oxidation of glycerol with molecular oxygen in base-free aqueous solutions has become a hot topic,as the rapidly increasing production of biodiesel is creating a surplus of glycerol.In this work,an N-doped-carbon-supported core-shell structured Sb@PtSb2 hybrid catalyst was prepared via a facile synthesis route,in which a mixture of glucose,melamine,and SbCl3(Sb-NC)was pyrolyzed,then impregnated with Pt by immersion in an aqueous solution of H2PtCl6,and further treated in hydrogen flow.Characterization of the catalyst products indicated that introducing SbCl3 can increase the surface area of the binary glucose+melamine pyrolyzed support(NC),and Sb@PtSb2 hybrids could be formed on the surface of an Sb-NC support during hydrogen treatment at 700℃.It was found that the Sb@PtSb2/NC catalyst was more active for the selective oxidation of glycerol in a base-free aqueous solution than Sb-free NC-supported Pt(Pt/NC).Further characterization also indicated that the promising performance of Sb@PtSb2/NC might be attributed to its enhanced oxygen activation.
基金financially supported by the Natural Science Foundation of China (21776077)the Shanghai Natural Science Foundation (17ZR1407300 and 17ZR1407500)+5 种基金the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learningthe Shanghai Rising-Star Program (17QA1401200)the Open Project of State Key Laboratory of Chemical Engineering (SKLChe-15C03)the State Key Laboratory of Organic– Inorganic Composites (oic-201801007)the Fundamental Research Funds for the Central Universities (222201718003)the 111 Project of the Ministry of Education of China (B08021)
文摘Understanding the nature of Pt active sites is of great importance for the structure-sensitive base-free oxidation of glycerol. In the present work, the remarkable Pt particle size effects on glycerol conversion and products formation from the oxidation of the primary and the secondary hydroxyl groups are understood by combining the model calculations and DFT calculations, aiming to discriminate the corresponding dominant Pt active sites. The Pt(100) facet is demonstrated to be the dominant active sites for the glycerol conversion and the products formation from the two routes. The insights revealed here could shed new light on fundamental understanding of the Pt particle size effects and then guiding the design and optimization of Pt-catalyzed base-free oxidation of glycerol toward targeted products.
基金supported by the National Natural Science Foundation of China(21606219)the “Transformational Technologies for Clean Energy and Demonstration”,Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21030900)~~
文摘The design and preparation of suitable supports are of great importance for gold catalysts to attain excellent catalytic performance for alcohol oxidation.In this work,we found that ZnO-CuO mixed oxides supported gold catalysts showed much better catalytic activity for base-free aerobic oxidation of benzyl alcohol than Au/ZnO and Au/CuO catalysts,and among them Au/Zn0.7Cu0.3O displayed the best catalytic performance.In addition,the Au/Zn0.7Cu0.3O catalyst could selectively catalyze the aerobic oxidation of a wide range of alcohols to produce the corresponding carbonyl compounds with high yields under mild conditions without base.Further characterizations indicated that the outstanding catalytic performance of Au/Zn0.7Cu0.3O was correlated with the small size of Au nanoparticles(NPs),good low-temperature reducibility,high concentration of surface oxygen species,and collaborative interaction between Au NPs and mixed oxide.
基金Financial support from the National Science Foundation of China (No. 21202049)the Recruitment Program of Global Experts (1000 Talents Plan)+2 种基金Fujian Hundred Talents PlanProgram of Innovative Research Team of Huaqiao UniversityInstrumental Analysis Center of Huaqiao University for analysis support
文摘An efficient copper-catalyzed decarboxylative hydroboration of phenylpropiolic acids with bis（pinacolato）diboron was developed, affording b-vinylboronates as the only products in high yields. Extra hydrogen sources such as methanol are not needed in this catalytic system. This reaction could be performed successfully under ligand- and base-free conditions. It demonstrated that phenylpropiolic acids can be employed as alkyne synthons in the hydroboration reaction and exhibited good reactivity and higher selectivity than terminal alkynes.
基金supported by the National Natural Science Foundation of China (20533080)
文摘A base-free catalyst system Co(acac)3/BMMImCl was developed for the carbonylation of amines with CO2.45%-81% isolated yields for N,N'-dialkylureas and 6%-23% isolated yields for N,N-diarylureas were obtained.The catalyst system was recovered and reused without significant loss in activity.In this catalyst system,the base catalyst and chemical dehydrant were efficiently avoided.Different reaction conditions were also discussed and a postulated mechanism was proposed.
基金supported by the National Youth Talent Support Program,National Natural Science Foundation of China(No.31971614)State Key Laboratory of Pulp and Paper Engineering(No.2022PY02)+3 种基金the National Program for Support of Topnotch Young Professionals(No.x2qsA4210090)Guangdong Basic and Applied Basic Research Foundation(Nos.2021A1515110205,2021A1515110622,2021A1515110245 and 2020A1515110705)Science and Technology Basic Resources Investigation Program of China(No.2019FY100900)the National Key Research and Development Program of China(No.2021YFC2101604).
文摘Selective oxidation of biomass-derived monosaccharide into high value-added chemicals is highly desirable from sustainability perspectives.Herein,we demonstrate a surface-functionalized carbon nanotubesupported gold(Au/CNT-O and Au/CNT-N)catalyst for base-free oxidation of monosaccharide into sugar acid.Au/CNT-O and Au/CNT-N surfaces successfully introduced oxygen-and nitrogen-containing functional groups,respectively.The highest yields of gluconic acid and xylonic acid were 93.3%and 94.3%,respectively,using Au/CNT-N at 90℃ for 240 min,which is higher than that of using Au/CNT-O.The rate constants for monosaccharide decomposition and sugar acid formation in Au/CNT-N system were higher,while the corresponding activation energy was lower than in Au/CNT-O system.DFT calculation revealed that the mechanism of glucose oxidation to gluconic acid involves the adsorption and activation of O_(2),adsorption of glucose,dissociation of the formyl C-H bond and formation of O-H bond,and formation and desorption of gluconic acid.The activation energy barrier for the glucose oxidation over Au/CNT-N is lower than that of Au/CNT-O.The nitrogen-containing functional groups are more beneficial for accelerating monosaccharide oxidation and enhancing sugar acid selectivity than oxygen-containing functional groups.This work presents a useful guidance for designing and developing highly active catalysts for producing high-value-added chemicals from biomass.
基金supported by the National Natural Science Foundation of China(Grant No.21203102)the Nankai University&Cangzhou Bohai New Area Institute of Green Chemical Engineering Fund(Grant No.NCC2020PY02)+2 种基金the Tianjin Municipal Natural Science Foundation(Grant No.17JCYBJC22600)the Innovative Team Project of Ministry of Education of China(IRT13R30)the Fundamental Research Funds for the Central Universities.
文摘A base-free catalytic system for the aerobic oxidation of 5-hydroxymethyl-2-furfural was exploited by using Pt nanoparticles immobilized onto a thermoresponsive poly(acrylamide-co-acrylonitrile)-b-poly(N-vinylimidazole)block copolymer,with an upper critical solution temperature of about 45°C.The Pt nanocatalysts were well-dispersed and highly active for the base-free oxidation of 5-hydroxymethyl-2-furfural by molecular oxygen in water,affording high yields of 2,5-furandicarboxylic acid(up to>99.9%).The imidazole groups in the block copolymer were conducive to the improvement of catalytic performance.Moreover,the catalysts could be easily separated and recovered based on their thermosensitivity by cooling the reaction system below the upper critical solution temperature.Good stability and reusability were observed over these copolymer-immobilized catalysts with no obvious decrease in catalytic activity in the five consecutive cycles.
基金supported by the National Natural Science Foundation of China (Nos.51836006,U1609212)Key Research and Development Project of Shandong Province (No.2019JZZY010403)。
文摘CeO_(2) morphology was proposed to be a crucial factor for reducing nitrobenzene to azoxybenzene under the base-free condition.Herein,the structure-activity relationship of CeO_(2) catalysts was explored to improve the azoxybenzene yield.A series of CeO_(2) catalysts we re synthesized with seven morphologies to obtain different Ce^(3+) proportion and various surface areas.Notably,the catalytic performance of these samples for reducing nitrobenzene to azoxybenzene enhanced with the increasing Ce^(3+) proportio n.With the highest surface Ce^(3+) proportion,the Rod-CeO_(2) catalyst exhibited 100% conversion of nitrobenzene and 89.8% azoxybenzene selectivity in 7 h at 150℃ under 1 MPa CO.Moreover,the preliminary mechanistic analysis indicated that the inhabitation of azoxybenzene to by-product azobenzene resulted in the high selectivity of azoxybenzene.
