Xu Xinyue, Liu He, Li Dongdong, Wang Qicheng, Zhu Xianjun, Liu Dongming, Chen Xiang
School of Materials Science and Engineering, Anhui University of Technology, Maanshan 243002, PR China.
College of Electronic and Optical Engineering and College of Microelectronics, Nanjing University of Posts and Telecommunications, Nanjing 210023, PR China.
J Colloid Interface Sci. 2023 Nov 15;650(Pt A):498-505. doi: 10.1016/j.jcis.2023.07.006. Epub 2023 Jul 3.
The adsorption energy of oxygen-containing intermediates for the oxygen evolution reaction (OER) electrocatalysts plays a key role on their electrocatalytic performances. Rational optimization and regulation of the binding energy of intermediates can effectively improve the catalytic activities. Herein, the binding strength of Co phosphate to *OH was weakened by generating lattice tensile strain via Mn replacement, which modulated the electronic structure and optimized the reactive intermediates adsorption with active sites. The tensile-strained lattice structure and stretched interatomic distance were confirmed by X-ray diffraction and extended X-ray absorption fine structure (EXAFS) spectra measurements. The as-obtained Mn-doped Co phosphate exhibits excellent OER activity with an overpotential of 335 mV at 10 mA cm, which is much higher than pristine Co phosphate. In-situ Raman spectra and methanol oxidation reaction experiments demonstrated that Mn-doped Co phosphate with lattice tensile strain shows optimized *OH adsorption strength, and is favorable to structure reconstruction and form highly active Co oxyhydroxide intermediate during OER process. Our work provides insight into the effects of the lattice strain on the OER activity from the standpoint of intermediate adsorption and structure transformation.
析氧反应(OER)电催化剂中含氧中间体的吸附能对其电催化性能起着关键作用。合理优化和调节中间体的结合能可以有效提高催化活性。在此,通过Mn取代产生晶格拉伸应变,减弱了磷酸钴与OH的结合强度,从而调节了电子结构并优化了活性位点对反应中间体的吸附。通过X射线衍射和扩展X射线吸收精细结构(EXAFS)光谱测量证实了拉伸应变的晶格结构和拉长的原子间距离。所制备的Mn掺杂磷酸钴表现出优异的OER活性,在10 mA cm时过电位为335 mV,远高于原始磷酸钴。原位拉曼光谱和甲醇氧化反应实验表明,具有晶格拉伸应变的Mn掺杂磷酸钴表现出优化的OH吸附强度,有利于OER过程中的结构重构并形成高活性的羟基氧化钴中间体。我们的工作从中间体吸附和结构转变的角度深入了解了晶格应变对OER活性的影响。