仿氢化酶活性中心结构的二氧化碳加氢催化剂计算设计
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- 英文论文题名：Computational Design of Iron Complexes for Catalytic Hydrogenation of Carbon Dioxide: A Mimic of Hydrogenases
- 论文作者：陈向洋 ; 杨新征
- 英文论文作者：Xiangyang Chen ; Xinzheng Yang ; Institute of Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院化学研究所;
- 论文关键词：计算设计 ; 铁催化剂 ; 二氧化碳加氢 ; 甲醇 ; 氢化酶
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O643.36
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：217k
- 原文格式：D
- 会议级别：全国
摘要
二氧化碳催化加氢反应是二氧化碳转化利用中最重要的核心问题。特别是二氧化碳加氢制甲醇的反应,不仅仅是一种将二氧化碳转化为二次能源的途径,同时也由于甲醇的高含氢量(12.6 wt%)和易输运性而成为一种非常有前景的储氢方式。我们在了解氢化酶催化氢分子活化与质子还原反应机理的基础上,参考其活性中心结构,利用实验上已合成的配体,构建了一系列含吊坠氨结构的新型铁配合物(P~(tBu)_2N~(tBu)_2)FeH(CO)_2R(R=H,Cl,NO_2,CN,C_5H_4N,CH_3,NH_2,OCH_3,OH,CHO,COOH,COCH_3,COOCH_3,CONHCOOH and CONH_2),并计算预测了这些配合物的化学稳定性,以及它们催化二氧化碳加氢制甲醇反应的可行性~([1])。我们发现R为给电子配体时往往具有较低的反应能垒。特别是R=COOH时,反应总能垒仅为23.7 kcal/mol。因此,我们计算设计的这一系列铁配合物极有潜力发展成为高效、廉价的二氧化碳加氢制甲醇反应催化剂。
Inspired by the active site structures of hydrogenases, we built a series of iron dicarbonyl diphosphine complexes with pendant amines,(P~(tBu)_2N~(tBu)_2)FeH(CO)_2R(R = H, Cl, NO_2, CN, C_5H_4N, CH_3, NH_2, OCH_3, OH, CHO, COOH, COCH_3, COOCH_3, CONH_2 and CONHCOOH), and predicted their potentials to catalyze the hydrogenation of CO_2 to methanol using the density functional theory.We found that the iron complexes with electron donor groups at R usually have lower barriers.Among the proposed iron complexes, the one with R = COOH has a total free energy barrier of 23.7 kcal/mol.Such a low barrier indicates that our computationally designed iron complexes are is a very promising low-cost catalyst for high efficiency conversion of CO_2 and H_2 to methanol under mild conditions.
Inspired by the active site structures of hydrogenases, we built a series of iron dicarbonyl diphosphine complexes with pendant amines,(P~(tBu)_2N~(tBu)_2)FeH(CO)_2R(R = H, Cl, NO_2, CN, C_5H_4N, CH_3, NH_2, OCH_3, OH, CHO, COOH, COCH_3, COOCH_3, CONH_2 and CONHCOOH), and predicted their potentials to catalyze the hydrogenation of CO_2 to methanol using the density functional theory.We found that the iron complexes with electron donor groups at R usually have lower barriers.Among the proposed iron complexes, the one with R = COOH has a total free energy barrier of 23.7 kcal/mol.Such a low barrier indicates that our computationally designed iron complexes are is a very promising low-cost catalyst for high efficiency conversion of CO_2 and H_2 to methanol under mild conditions.
引文
[1]Chen,X.;Yang,X.J.Phys.Chem.Lett.2016,7:1035.