Mengting Zhou, Hongxia Liu, Juntao Yan, Qingjun Chen, Rong Chen, Lei Liu
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引用次数: 0
摘要
金属铋既无毒又具有成本效益。铋基催化剂已证明能够通过 CO2RR 高效地产生 HCOOH,同时有效抑制 HER。虽然已有许多关于其 CO2 还原性能的实验报告,但其价态和晶面对 CO2RR 选择性(如 HCOOH 与 CO)的影响仍有待商榷。在这里,我们通过密度泛函理论进行了全面研究,包括 Bi 的三种典型价态,如 0(Bi)、+3(Bi2O3)和+5(Bi2O5),以及经常研究的晶面。研究结果表明,金属 Bi 对 HCOOH 的选择性较差,但对 CO2 的转化率较高。Bi2O3 对 HCOOH 的生成具有良好的选择性,但对 CO2 的转化率较低。对于 Bi2O5,所有研究的表面在 HCOOH 和 CO 生成两种情况下都显示出较高的能垒,而在 HER 反应中则显示出较低的能垒,这表明+5 价态的 Bi 不是 2e 转移反应的良好选择。有趣的是,我们发现 Bi 的部分氧化对选择性和转化率都有好处。根据这些观察结果,我们认为在未来的实验中,Bi (0) 和 Bi2O3(+3) 的混合物将是比单晶体更好的选择。
On the electrochemical CO2 reduction by Bi-based catalysts: single crystals or mixture phases
Metallic bismuth is both non-toxic and cost-effective. Bi-based catalysts
have demonstrated the ability to efficiently produce HCOOH through CO2RR while
effectively inhibiting the HER. Although many experiments have been reported
concerning its performance towards CO2 reduction, the impact its valence states
and crystal faces on CO2RR selectivity (e.g. HCOOH versus CO) it still under
debate. Here, we performed a comprehensive study via density functional theory,
by including three typical valence states of Bi, such as 0 (Bi), +3 (Bi2O3) and
+5 (Bi2O5), as well as their often-studied crystal facets. The results show
that metallic Bi demonstrates a poor selectivity for HCOOH, but boasts a higher
conversion rate for CO2. While Bi2O3 exhibits a good selectivity for HCOOH
production, yet it displays a lower conversion rate for CO2. For Bi2O5, all
studied surfaces show high energy barriers in both cases of HCOOH and CO
production, and lower energy barriers for HER reactions, indicating that Bi at
+5 valence state is not the good choice for 2e transfer reactions.
Subsequently, we further examined the effects of oxygen contents on the
selectivity of HCOOH and the conversion rate for CO2. Interestingly, we found
that partial oxidization of Bi benefits both the selectivity and the conversion
rate. With these observations, we suggest that a mixture of Bi (0) and Bi2O3
(+3) phases would be a better choice than single crystals for future
experiments.