The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts rem...The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.展开更多
报道了中试规模制备L-茶氨酸和L-谷氨酰胺的一种方法。以廉价的L-谷氨酸为原料,采用邻苯二甲酰基作为保护基,保护L-谷氨酸的α-氨基,醋酐回流10 m in使其分子内脱水生成N-邻苯二甲酰-L-谷氨酸酐,在常温、常压条件下,分别与2 mol/L氨水和...报道了中试规模制备L-茶氨酸和L-谷氨酰胺的一种方法。以廉价的L-谷氨酸为原料,采用邻苯二甲酰基作为保护基,保护L-谷氨酸的α-氨基,醋酐回流10 m in使其分子内脱水生成N-邻苯二甲酰-L-谷氨酸酐,在常温、常压条件下,分别与2 mol/L氨水和2 mol/L乙胺水溶液反应生成中间产物N-邻苯二甲酰-L-谷氨酰胺、N-邻苯二甲酰-L-茶氨酸,中间产物在室温条件下与0.5 mol/L水合肼反应48 h脱除保护基,分别以57%、61%的收率得到L-谷氨酰胺和L-茶氨酸。展开更多
The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the ...The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the proportion of mixed emulsifiers, the dosage of emulsifiers as well as the preparation methods of water-in-oil emulsion on monomer conversion, grafting ratio, and specific viscidity is discussed. The result indicates that calcium oleate or magnesium oleate as the emulsifier is better than sodium oleate or potassium oleate, and the mixture of oleic acid and its salt is better than any single compound.It is also concluded that monomer conversion reaches 99.7% and grafting ratio reaches 98.4% when m(oleic acid)/m(oleate sodium) is 60/40,m(starch)/m(monomers) is 1/1(among the monomers m(AM)/m(AA) is 4/1),v(oil phase)/v(water phase) is 1.2/1, initiator concentration is 2.4×10 -4mol·L -1,reaction temperature is 45～50℃,and reaction time is 6 hours.When mixed emulsifers concentration is 6%, the intrinsic viscidity reaches 1100ml·g -1.展开更多
基金financially supported by the Sichuan Science and Technology Program (Grant No. 2025NSFSC0139)the China Postdoctoral Science Foundation (Grant No.2023MD734228)+10 种基金funding from Generalitat de Catalunya 2021SGR00457supported by MCIN with funding from European Union NextGenerationEU(PRTR-C17.I1)by Generalitat de Catalunya (In-CAEM Project)the support from the project AMaDE(PID2023-149158OB-C43)funded by MCIN/AEI/10.13039/501100011033/by “ERDF A way of making Europe”by the “European Union”supported by the Severo Ochoa program from Spanish MCIN/AEI (Grant No.:CEX2021-001214-S)funded by the CERCA Programme/Generalitat de Catalunyaperformed in the framework of Universitat Autònoma de Barcelona Materials Science PhD programfunding from the CSC-UAB PhD scholarship program. ICN2 is founding member of e-DREAM[87]
文摘The methanol oxidation reaction(MOR)to formic acid offers a promising alternative to the anodic oxygen evolution reaction(OER)in water electrolysis.However,the development of efficient and cost-effective catalysts remains a primary challenge.In this study,an enhancement in catalytic MOR performance is achieved through the incorporation of Mn atoms with unsaturated t_(2g)orbitals into Ni_(3)Se_(4).Comprehensive experimental analyses and theoretical calculations reveal that substituting Ni with Mn induces strong electron-withdrawing effects,effectively modulating the local coordination environment of the metal centers.The presence of Mn also elongates Ni–Se(O)bonds,which reduces eg orbital occupancy and modifies the spin state of the material.Electrochemical measurements demonstrate that electrodes based on this optimized material exhibit a high spin state and deliver excellent catalytic activity,achieving a MOR current density up to∼190 mA cm^(−2)at 1.6 V.This performance enhancement is attributed to the favorable electronic configuration and reduced reaction energy barriers associated with the high-spin state.
文摘The effect of oleates as emulsifiers on graft copolymerization of starch with acrylamide (AM) and acrylic acid (AA) in the inverse emulsion system is studied in this paper .The effect of the kinds of emulsifiers, the proportion of mixed emulsifiers, the dosage of emulsifiers as well as the preparation methods of water-in-oil emulsion on monomer conversion, grafting ratio, and specific viscidity is discussed. The result indicates that calcium oleate or magnesium oleate as the emulsifier is better than sodium oleate or potassium oleate, and the mixture of oleic acid and its salt is better than any single compound.It is also concluded that monomer conversion reaches 99.7% and grafting ratio reaches 98.4% when m(oleic acid)/m(oleate sodium) is 60/40,m(starch)/m(monomers) is 1/1(among the monomers m(AM)/m(AA) is 4/1),v(oil phase)/v(water phase) is 1.2/1, initiator concentration is 2.4×10 -4mol·L -1,reaction temperature is 45～50℃,and reaction time is 6 hours.When mixed emulsifers concentration is 6%, the intrinsic viscidity reaches 1100ml·g -1.
