Xie Ruikuan, Hou Zhufeng, Chai Guo-Liang
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences (CAS), Fuzhou 350002 Fujian, People's Republic of China.
J Chem Phys. 2022 Aug 21;157(7):074704. doi: 10.1063/5.0100268.
Developing efficient catalysts for electrochemical CO reduction reaction (ECORR) to hydrocarbons is becoming increasingly important but still challenging due to their high overpotential and poor selectivity. Here, the famous Heusler alloys are investigated as ECORR catalysts for the first time by means of density functional theory calculations. The linear scaling relationship between the adsorption energies of CHO (and COOH) and CO intermediates is broken and, thus, the overpotential can be tuned regularly by chemically permuting different 3d, 4d, or 5d transition metals (TMs) in Heusler alloy CuTMAl. CuZnAl shows the best activity among all the 30 Heusler alloys considered in the present study, with 41% improvement in energy efficiency compared to pure Cu electrode. CuPdAl, CuAgAl, CuPtAl, and CuAuAl are also good candidates. The calculations on the competition between hydrogen evolution reaction and CORR indicate that CuZnAl is also the one having the best selectivity toward hydrocarbons. This work identifies the possibility of applying the Heusler alloy as an efficient ECORR catalyst. Since thousands of Heusler alloys have been found in experiments, the present study also encourages the search for more promising candidates in this broad research area.
开发用于电化学CO还原反应（ECORR）生成碳氢化合物的高效催化剂变得越来越重要，但由于其高过电位和低选择性，这仍然具有挑战性。在此，首次通过密度泛函理论计算研究了著名的赫斯勒合金作为ECORR催化剂的情况。CHO（和COOH）与CO中间体吸附能之间的线性标度关系被打破，因此，通过化学置换赫斯勒合金CuTMAl中不同的3d、4d或5d过渡金属（TM），可以定期调节过电位。在本研究考虑的所有30种赫斯勒合金中，CuZnAl表现出最佳活性，与纯铜电极相比，能量效率提高了41%。CuPdAl、CuAgAl、CuPtAl和CuAuAl也是不错的候选材料。析氢反应与CORR之间竞争的计算表明，CuZnAl对碳氢化合物也具有最佳选择性。这项工作确定了将赫斯勒合金用作高效ECORR催化剂的可能性。由于在实验中已发现数千种赫斯勒合金，本研究也鼓励在这一广泛的研究领域中寻找更有前景的候选材料。
