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Ultrafine Pt nanoparticles supported on double-shelled C/TiO2 hollow spheres material as highly efficient methanol oxidation catalysts 被引量:5
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作者 xiaoyu yue Yuguang Pu +2 位作者 Wen Zhang Ting Zhang Wei Gao 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2020年第10期275-282,共8页
Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination o... Catalyst support is extremely important for future fuel cell devices.In this work,we developed doubleshelled C/TiO2(DSCT)hollow spheres as an excellent catalyst support via a template-directed method.The combination of hollow structure,TiO2 shell and carbon layer results in excellent electron conductivity,electrocatalytic activity,and chemical stability.These uniformed DSCT hollow spheres are used as catalyst support to synthesize Pt/DSCT hollow spheres electrocatalyst.The resulting Pt/DSCT hollow spheres exhibited high catalytic performance with a current density of 462 mA mg^-1 for methanol oxidation reaction,which is 2.52 times higher than that of the commercial Pt/C.Furthermore,the increased tolerance to carbonaceous poisoning with a higher If/Ibratio and a better long-term stability in acid media suggests that the DSCT hollow sphere is a promising C/TiO2-based catalyst support for direct methanol fuel cells applications. 展开更多
关键词 Catalyst support C/TiO2 hollow sphere Metal-support interactions Methanol oxidation reaction
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阴离子协助镍催化碳氟键官能团化反应机理研究 被引量:2
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作者 曾珍 张涛 +3 位作者 岳小雨 张华 白若鹏 蓝宇 《中国科学:化学》 CAS CSCD 北大核心 2018年第7期736-742,共7页
由于碳-氟键的化学惰性,其高效催化转化一直是有机化学中的难题之一.本文运用密度泛函理论(DFT)计算,研究了镍催化碳-氟/碳-氢键交叉偶联反应构建2-芳基噁唑衍生物的机理.计算结果表明,体系中氟负离子能够稳定零价镍金属催化剂,得到氟... 由于碳-氟键的化学惰性,其高效催化转化一直是有机化学中的难题之一.本文运用密度泛函理论(DFT)计算,研究了镍催化碳-氟/碳-氢键交叉偶联反应构建2-芳基噁唑衍生物的机理.计算结果表明,体系中氟负离子能够稳定零价镍金属催化剂,得到氟负离子配位的阴离子镍活性催化物种.在氟负离子协助下碳-氟键对阴离子镍氧化加成得到二价芳基镍物种,是催化循环的速控步骤.在碳氢键切断过程中,Br?nsted碱直接进攻去质子,得到二芳基镍中间体,最终通过还原消除得到交叉偶联产物.在这一过程中,阴离子镍活性催化物种的稳定性明显高于通常推测的中性镍催化物种,这一模型为理解惰性碳-氟键活化反应机理提供了新的思路. 展开更多
关键词 碳-氟键 密度泛函理论 氟负离子协助 阴离子镍
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Theoretical insight into phosphoric acid-catalyzed asymmetric conjugate addition of indolizines to a,β-unsaturated ketones
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作者 Haohua Chen Lei Zhu +4 位作者 Kangbao Zhong xiaoyu yue Ling-Bo Qu Ruopeng Bai Yu Lan 《Chinese Chemical Letters》 SCIE CAS CSCD 2018年第8期1237-1241,共5页
Phosphoric acid catalysis is a powerful tool for the construction of new CààC bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyze... Phosphoric acid catalysis is a powerful tool for the construction of new CààC bonds because of its unique LUMO-lowering activity. Theoretical calculations were employed to investigate phosphoric acidcatalyzed asymmetric conjugate addition of indolizines to a,b-unsaturated ketones. The calculation results showed that this transformation proceeds via a reaction pathway involving nucleophilic addition,deprotonation–aromatization, and tautomerization. The computational results showed that deprotonation–aromatization is the rate-determining step and the enantioselectivity-determining step.The S-configured product was preferentially generated via a pathway starting from the s-cis conjugated ketone, whereas the s-trans isomer led to a side product with the R configuration. Non-covalent interaction analysis showed that the enantioselectivity is mainly caused by bond-rotation strain in the transition states of the deprotonation–aromatization step. 展开更多
关键词 Phosphoric acid catalysis Theoretical calculations MECHANISM ENANTIOSELECTIVITY
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