College of Chemical and Environmental Engineering, State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of Science and Technology, Shandong University of Science and Technology, Qingdao 266590, China.
College of Chemistry and Molecular Engineering, Key Laboratory of Optic-electric Sensing and Analytical Chemistry for Life Science, MOE, Shandong Key Laboratory of Biochemical Analysis, Qingdao University of Science and Technology, Qingdao 266042, China.
J Colloid Interface Sci. 2020 Mar 1;561:881-889. doi: 10.1016/j.jcis.2019.11.071. Epub 2019 Nov 18.
The development of low-cost noble metal-free and high-active electrocatalysts for methanol electrooxidation is highly worthwhile but remains a challenge. In this paper, 5, 10, 15, 20-tetrakis(4-carboxylphenyl)porphyrin (HTCPP) modified nickel-cobalt layer double hydroxides nanosheets (NiCo-LDH) were prepared by one-pot hydrothermal method and characterized by the powder X-ray diffraction (XRD), the scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS), etc. HTCPP/NiCo-LDH was demonstrated as superior a photoelectrocatalyst towards methanol oxidation in the alkaline media. Due to the introduction of HTCPP photosensitizer, HTCPP/NiCo-LDH exhibits the outstanding photoeletrocatalytic activity toward methanol oxidation under the visible-light irradiation. The great enhancement in the photoelectrocatalytic activity are attributed to high exposed surface active sites, efficient widen adsorption wavelength of HTCPP in visible region, as well as efficient electron transfer between the electrode surface and the active sites. The HTCPP/NiCo-LDH nanosheets show mass activity of 246.6 mA mg and specific activity of 34.9 mA cm for methanol oxidation under visible-light, which are 2.32 times higher than that of NiCo-LDH at the same conditions. The developing catalytic activity of HTCPP/NiCo-LDH for methanol oxidation are attributed to the synergistic effect of HTCPP and NiCo-LDH. This study may offer new ideas for developing highly effective noble metal-free catalysts for the application in methanol oxidation.
开发低成本、无贵金属和高活性的甲醇电氧化电催化剂是非常值得的，但仍然是一个挑战。本文采用一步水热法制备了 5,10,15,20-四(4-羧基苯基)卟啉(HTCPP)修饰的镍钴层状双氢氧化物纳米片( NiCo-LDH)，并通过粉末 X 射线衍射(XRD)、扫描电子显微镜(SEM)和 X 射线光电子能谱(XPS)等对其进行了表征。HTCPP/NiCo-LDH 被证明是一种在碱性介质中对甲醇氧化具有优异光电催化性能的催化剂。由于引入了 HTCPP 光敏剂，HTCPP/NiCo-LDH 在可见光照射下表现出对甲醇氧化的优异光电催化活性。光电催化活性的显著提高归因于高暴露的表面活性位点、HTCPP 在可见光区有效拓宽的吸附波长，以及电极表面和活性位点之间的有效电子转移。HTCPP/NiCo-LDH 纳米片在可见光下对甲醇氧化的质量活性为 246.6 mA mg，比相同条件下的 NiCo-LDH 高 2.32 倍，比 NiCo-LDH 高 2.32 倍。HTCPP/NiCo-LDH 对甲醇氧化的催化活性提高归因于 HTCPP 和 NiCo-LDH 的协同效应。这项研究为开发用于甲醇氧化的高效无贵金属催化剂提供了新的思路。
