关于吡啶催化二氧化碳还原反应的理论研究
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- 英文论文题名：Theoretical Insights into Pyridinium Catalyzed CO_2 Reduction
- 论文作者：范雪婷 ; 贾玫 ; 程俊
- 英文论文作者：Xueting Fan ; Mei Jia ; Jun Cheng ; Department of Chemistry ; University of Xiamen ; College of Chemistry and Chemical Engineering
- 年：2016
- 作者机构：厦门大学;
- 论文关键词：氧化还原电位 ; DFTMD ; 电极表面
- 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-第十五分会：表界面结构调控与催化
- 语种：中文
- 分类号：O643.32
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十五分会 ; 表界面结构调控与催化
- 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：216k
- 原文格式：D
- 会议级别：全国
摘要
实验证据表明,吡啶可以催化二氧化碳还原反应。通常认为,PyH~●是催化这一反应的活性物种[1]。我们使用一种基于密度泛函理论的分子动力学模拟方法[2](DFTMD)计算均相中质子化吡啶的还原电位(-1.87V vs SHE),与实验测得的开路电位(-0.34V vs SHE)差别约为1.5V,这一结果支持以前文献中理论计算[3]的结论:在均相中,质子化吡啶的还原不是二氧化碳还原反应的决速步。我们的计算结果与文献计算值[3]差别也比较大(~0.7V)。可能的原因为隐式溶剂化模型没有考虑溶剂水的电子结构的影响。近年来的研究发现,溶质能级和溶剂水的能带之间的杂化会对氧化还原电位的计算产生很大的影响。目前,我们也用HSE06泛函进行了计算,来改善BLYP泛函的离域误差。我们也考虑了Ga P电极表面[4]的影响。首先,我们使用DFTMD方法和PBE泛函计算了在Ga P(110的能带位置。结果发现,溶剂水会对Ga P(110)表面的电子结构产生较大的影响。同时,将计算得到的Ga P(110)的CBM与均相中质子化吡啶的还原电位进行比较,发现激发的电子不太容易从Ga P(110)的CBM转移到溶液中的质子化吡啶。接下来,我们将对相关活性物种在表面的吸附情况进行研究。
We calculated the redox potential of pyridinium using a new method based on density functional theory based molecular dynamics(DFTMD) that treats the solute and solvent at the same level of electronic structure theory.The redox potential of pyridinium we obtained(-1.87 V vs SHE) gives support to the claim from the previous theoretical work that PyH~● is unlikely to be the active species in reducing CO_2 in homogeneous solution.We are currently running the calculation using a hybrid functional(HSE06).The role of Ga P photocathodes in pyridinium-catalyzed CO_2 reduction is also studied.The electronic energy levels of a model Ga P/H2 O interface are computed using the PBE density functional.The interaction with water affect the electronic energy levels of the Ga P(110) surface significantly.Results show that reduction of pyridinium could not occur by transfer of photoexcited electrons from the Ga P photocathode.Now we are working on whether the redox potential could be reduced by pyridinium adsorption on the Ga P surface.
We calculated the redox potential of pyridinium using a new method based on density functional theory based molecular dynamics(DFTMD) that treats the solute and solvent at the same level of electronic structure theory.The redox potential of pyridinium we obtained(-1.87 V vs SHE) gives support to the claim from the previous theoretical work that PyH~● is unlikely to be the active species in reducing CO_2 in homogeneous solution.We are currently running the calculation using a hybrid functional(HSE06).The role of Ga P photocathodes in pyridinium-catalyzed CO_2 reduction is also studied.The electronic energy levels of a model Ga P/H2 O interface are computed using the PBE density functional.The interaction with water affect the electronic energy levels of the Ga P(110) surface significantly.Results show that reduction of pyridinium could not occur by transfer of photoexcited electrons from the Ga P photocathode.Now we are working on whether the redox potential could be reduced by pyridinium adsorption on the Ga P surface.
引文
[1]Barton Cole,E.;Lakkaraju,P.S.;Rampulla,D.M.;Morris,A.J.;Abelev,E.;Bocarsly,A.B.J.Am.Chem.Soc.2010,132:11539.
[2]Cheng,J.;Liu,X.;Vande Vondele,J.;Sulpizi,M.;Sprik,M.Acc Chem Res.2014,47:3522.
[3]Keith,J.A.;Carter,E.A.J.Am.Chem.Soc.2012,134:7580.
[4]Lessio,M.;Carter,E.A.J.Am.Chem.Soc.2015,137:13248.
[2]Cheng,J.;Liu,X.;Vande Vondele,J.;Sulpizi,M.;Sprik,M.Acc Chem Res.2014,47:3522.
[3]Keith,J.A.;Carter,E.A.J.Am.Chem.Soc.2012,134:7580.
[4]Lessio,M.;Carter,E.A.J.Am.Chem.Soc.2015,137:13248.