Studies on the use of renewable materials for various applications,including polymers,have gained momentum due to global climate change and the push towards a circular economy.In this study,polymer resins were develop...Studies on the use of renewable materials for various applications,including polymers,have gained momentum due to global climate change and the push towards a circular economy.In this study,polymer resins were developed through Michael 1,4-addition.The precursors were synthesized from tall oil-based acetoacetates derived from epoxidized tall oil fatty acids or their methyl esters.Two different epoxidation methods were employed:enzymatic epoxidation of tall oil fatty acids and ion-exchange resin epoxidation of tall oil fatty acid methyl esters.Following oxirane opening and transesterification with trimethylolpropane,further esterification or transesterification was carried out to obtain the acetoacetates.These synthesized acetoacetates were then reacted with acrylates of various functionalities to obtain polymer resins with differing degrees of crosslinking.The developed polymer resins were characterized using differential scanning calorimetry,dynamic mechanical analysis,and thermogravimetric analysis.The results indicated that the glass transition temperature and storage modulus of the polymer resins were significantly influenced by both the functionality of the acrylates used and the epoxidation technique employed.Higher acrylate functionality resulted in increased stiffness,while enzymatic epoxidation enhanced the polymer’s mechanical properties,nearly doubling the storage modulus,achieving approximately 470 MPa,compared to the ion-exchange resin technique.Therefore,selecting the appropriate acrylate functionality and epoxidation method could tailor the mechanical properties of the polymer resins.展开更多
Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemica...Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].展开更多
Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species for...Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.展开更多
Propylene oxide plays a pivotal role as an organic synthesis intermediate,boasting extensive downstream applications and promising market prospects.Propene epoxidation via molecular oxygen has garnered considerable at...Propylene oxide plays a pivotal role as an organic synthesis intermediate,boasting extensive downstream applications and promising market prospects.Propene epoxidation via molecular oxygen has garnered considerable attention due to its cost-effectiveness,environmental friendliness,ease of operation,and straightforward product separation.This paper provides an in-depth exploration of recent advance-ments,ranging from nanoparticle to Single-atom catalysts(SACs),in the context of propene epoxidation using molecular oxygen.Conventional nanoparticle catalysts,including those based on Ag,Cu,and other metals,are examined with regard to their contributions to support effects,electron effects,or crystal-plane effects within the mechanistic investigation.Furthermore,emerging SACs(specifically Mo,Cu,and Co)are discussed in terms of synthesis strategies,characterization methods,and mechanism studies.This comprehensive review sheds new light on design strategies,relevant characterizations,and thorough mechanism investigations aimed at fostering the development of efficient catalysts,thereby expediting progress in the industrial implementation of propene epoxidation.展开更多
The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variat...The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.展开更多
The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0....The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.展开更多
基金funded by the Latvian State Institute of Wood Chemistry Bioeconomic grant no.04-24“Development of Composites from Polymer Resin Synthesized from Tall Oil Fatty Acids and Reinforced with Various Fillers”(FiTeCo).
文摘Studies on the use of renewable materials for various applications,including polymers,have gained momentum due to global climate change and the push towards a circular economy.In this study,polymer resins were developed through Michael 1,4-addition.The precursors were synthesized from tall oil-based acetoacetates derived from epoxidized tall oil fatty acids or their methyl esters.Two different epoxidation methods were employed:enzymatic epoxidation of tall oil fatty acids and ion-exchange resin epoxidation of tall oil fatty acid methyl esters.Following oxirane opening and transesterification with trimethylolpropane,further esterification or transesterification was carried out to obtain the acetoacetates.These synthesized acetoacetates were then reacted with acrylates of various functionalities to obtain polymer resins with differing degrees of crosslinking.The developed polymer resins were characterized using differential scanning calorimetry,dynamic mechanical analysis,and thermogravimetric analysis.The results indicated that the glass transition temperature and storage modulus of the polymer resins were significantly influenced by both the functionality of the acrylates used and the epoxidation technique employed.Higher acrylate functionality resulted in increased stiffness,while enzymatic epoxidation enhanced the polymer’s mechanical properties,nearly doubling the storage modulus,achieving approximately 470 MPa,compared to the ion-exchange resin technique.Therefore,selecting the appropriate acrylate functionality and epoxidation method could tailor the mechanical properties of the polymer resins.
基金supported by the National Natural Science Foundation of China (29792072, 22278441, 22478452)National Key Research and Development Program of China (937) (2006CB202508)the SINOPEC Project (419019-2, 413108)。
文摘Propylene oxide(PO),with its reactive three-membered epoxide functional group,exhibits remarkable functional versatility and serves as a crucial bridge connecting the gaps between fossil energy utilization and chemical intermediate generation for new material innovation [1].For instance,PO's downstream derivatives,such as polyether polyols,carbonic esters,and polyurethanes,are widely utilized in wind power generation,battery electrolytes,solar cells,and CO_(2)-based degradable polymers,contributing to sustainable decarbonization in industry [2].
文摘Au sites supported on Ti-containing materials(Au/Ti-containing catalyst)are currently considered as a promising catalyst for the propylene epoxidation owing to the synergistic effect that hydrogen peroxide species formed on Au sites diffuses to the Ti sites to form the Ti-hydroperoxo intermedi-ates and contributes to the formation of propylene oxide(PO).In principle,thermal treatment will significantly affect the chemical and physical structures of Ti-containing materials.Consequently,the synergy between tailored Ti sites with different surface properties and Au sites is highly expected to enhance the catalytic performance for the reaction.Herein,we systematically studied the intrinsic effects of different microenvironments around Ti sites on the PO adsorption/desorption and conversion,and then effectively improved the catalytic performance by tailoring the number of surface hydroxyl groups.The Ti^(Ⅵ) material with fewer hydroxyls stimulates a remarkable enhancement in PO selectivity and H_(2) efficiency compared to the Ti^(Ⅵ) material that possessed more hydroxyls,offering a 7-fold and 4-fold increase,respectively.As expected,the Ti^(Ⅵ+Ⅳ) and Ti^(Ⅳ) materials also exhibit a similar phenomenon to the Ti^(Ⅵ) materials through the same thermal treatment,which strongly supports that the Ti sites microenvironment is an important factor in suppressing PO con-version and enhancing catalytic performance.These insights could provide guidance for the rational preparation and optimization of Ti-containing materials synergizing with Au catalysts for propylene epoxidation.
基金supported by the National Natural Science Foundation of China-Outstanding Youth foundation(No.22322814)National Natural Science Foundation of China(No.22108307,No.22108305)+1 种基金the National Natural Foundation of Shandong Province(ZR2021QB076,ZR2020YQ17,ZR2020KB006,ZR2023YQ009 and ZR2022MB015)the Fundamental Research Funds for the Central Universities(23CX04029 A).
文摘Propylene oxide plays a pivotal role as an organic synthesis intermediate,boasting extensive downstream applications and promising market prospects.Propene epoxidation via molecular oxygen has garnered considerable attention due to its cost-effectiveness,environmental friendliness,ease of operation,and straightforward product separation.This paper provides an in-depth exploration of recent advance-ments,ranging from nanoparticle to Single-atom catalysts(SACs),in the context of propene epoxidation using molecular oxygen.Conventional nanoparticle catalysts,including those based on Ag,Cu,and other metals,are examined with regard to their contributions to support effects,electron effects,or crystal-plane effects within the mechanistic investigation.Furthermore,emerging SACs(specifically Mo,Cu,and Co)are discussed in terms of synthesis strategies,characterization methods,and mechanism studies.This comprehensive review sheds new light on design strategies,relevant characterizations,and thorough mechanism investigations aimed at fostering the development of efficient catalysts,thereby expediting progress in the industrial implementation of propene epoxidation.
基金supported by Guangdong Science and Technology Planning Project(2015A020216002)Guangdong Natural Science Foundation(2014A030313259)the National Natural Science Foundation of China(21543014,21173086,U1301245)~~
文摘The heterogeneously copper-catalyzed oxidative cleavage of styrene was studied using copper-doped mesoporous KIT-6（CU-KIT-6_x） prepared via pH adjustment（where x is the pH：1.43,2.27,3.78,3.97,4.24 or 6.62）.Variations in the catalyst structure and morphology with pH values were characterized by X-ray power diffraction,nitrogen adsorption-desorption analysis,transmission electron microscopy and X-ray photoelectron spectroscopy.As the pH value applied during the initial synthesis,the resulting Cu-KIT-6_x exhibited different structural,textural and surface characteristics,especially in terms of specific copper species and copper content At a pH value of 3.78,approximately 4.6 wt%copper（Ⅱ） was successfully incorporated into the framework of the initial KIT-6,in the form of-Cu-O-Si- groups.The catalytic performance of each catalyst was evaluated by following the epoxidation of styrene,employing tert-butyl hydroperoxide as the oxidant and CH_3CN as the solvent.A significant styrene conversion of 43.5%with 86.6%selectivity for the desired styrene epoxide was obtained over the Cu-KIT-63.78.A higher Cu content,an ordered cubic laid mesoporous architecture and various specific textural characteristics all combined to endow the Cu-KIT-63.78 with high catalytic activity and good stability.
基金supported by the National Natural Science Foundation of China(21173100 and 21320102001)~~
文摘The catalytic epoxidation of olefin was investigated on two copper complex-modified molybdenum oxides with a 3D supramolecular structure, [Cu（bipy）]4[Mo15O47].2H2O （1） and [Cu1（bix）][（Cu1bix） （δ-MoVl8O26）0.5] （2） （bipy = 4,4＇-bipyridine, bix = 1,4-bis（imidazole-1-ylmethyl）benzene）. Both compounds were catalytically active and stable for the epoxidation of cyclooctene, 1-octene, and styrene with tert-butyl hydroperoxide （t-BuOOH） as oxidant. The excellent catalytic performance was attributed to the presence of stable coordination bonds between the molybdenum oxide and copper complex, which resulted in the formation of easily accessible Mo species with high electropositivity. In addition, the copper complex also acted as an active site for the activation of t-BuOOH, thus im- proving these copper complex-modified polyoxometalates.
