Rani Sonia, Nadeem Muhammad, Alrahili Mazen R, Shalash Marwan, Bhatti Moazzam H, Munawar Khurram Shahzad, Tariq Muhammad, Asif Hafiz Muhammad, El-Bahy Zeinhom M
Inorganic Research Laboratory, Institute of Chemical Sciences, Bahauddin Zakariya University Multan, 60800, Pakistan.
Department of Chemistry, Allama Iqbal Open University, Islamabad, Pakistan.
Dalton Trans. 2024 Jul 2;53(26):10875-10889. doi: 10.1039/d4dt00788c.
Electrocatalytic hydrogen generation in alkaline medium has become widely used in a variety of sectors. However, the possibility for additional performance improvement is hampered by slow kinetics. Because of this restriction, careful control over processes such as water dissociation, hydroxyl desorption and hydrogen recombination is required. Covalent organic frameworks (COFs) based on porphyrin and polyoxometalates (POMs) show encouraging electrocatalytic performance, offering a viable route for effective and sustainable hydrogen generation. Their specific architectures lead to increased electrocatalytic activity, which makes them excellent choices for developing water electrolysis as a clean energy conversion method in the alkaline medium. In this regard, TTris@ZnPor and Lindqvist POM were coordinated to create a new eco-friendly and highly active covalent organic framework (TP@VL-COF). In order to describe TP@VL-COF, extensive structural and morphological investigations were carried out through FTIR, H NMR, elemental analysis, SEM, fluorescence, UV-visible, PXRD, CV, N-adsorption isotherm, TGA and DSC analyses. In an alkaline medium, the electrocatalytic capability of 20%C/Pt, TTris@ZnPor, Lindqvist POM and TP@VL-COF was explored and compared for the hydrogen evolution reaction (HER). The TP@VL-COF showed the best catalytic efficiency for HER in an alkaline electrolyte, requiring just a 75 mV overpotential to drive 10 mA cm and outperforming 20%C/Pt, TTris@ZnPor, Lindqvist POM and other reported catalysts. The Tafel slope value also indicates faster kinetics for TP@VL-COF (114 mV dec) than for 20%C/Pt (182 mV dec) TTris@ZnPor (116 mV dec) and Lindqvist POM (125 mV dec).
碱性介质中的电催化析氢已在多个领域广泛应用。然而，缓慢的动力学阻碍了其性能的进一步提升。由于这一限制，需要仔细控制诸如水离解、羟基脱附和氢重组等过程。基于卟啉和多金属氧酸盐（POMs）的共价有机框架（COFs）展现出令人鼓舞的电催化性能，为高效且可持续的析氢提供了一条可行途径。其独特的结构导致电催化活性增强，使其成为在碱性介质中开发水电解作为清洁能源转换方法的理想选择。在这方面，通过将TTris@ZnPor与Lindqvist POM配位，创建了一种新型的环保且高活性的共价有机框架（TP@VL-COF）。为了描述TP@VL-COF，通过傅里叶变换红外光谱（FTIR）、核磁共振氢谱（H NMR）、元素分析、扫描电子显微镜（SEM）、荧光、紫外可见光谱、粉末X射线衍射（PXRD）、循环伏安法（CV）、氮吸附等温线、热重分析（TGA）和差示扫描量热法（DSC）分析进行了广泛的结构和形态研究。在碱性介质中，研究并比较了20%C/Pt、TTris@ZnPor、Lindqvist POM和TP@VL-COF对析氢反应（HER）的电催化能力。TP@VL-COF在碱性电解质中对HER表现出最佳的催化效率，驱动10 mA cm只需75 mV的过电位，优于20%C/Pt、TTris@ZnPor、Lindqvist POM以及其他已报道的催化剂。塔菲尔斜率值也表明TP@VL-COF（114 mV dec）的动力学比20%C/Pt（182 mV dec）、TTris@ZnPor（116 mV dec）和Lindqvist POM（125 mV dec）更快。
