Amorphous dominated metal hydroxide-organic framework with compositional and structural heterogeneity for enhancing anodic electro-oxidation reactions

Wenjun Tang; Zebin Yu; Honglei Chen; Ronghua Jiang; Jun Huang; Shuang Li; Yanping Hou; Mi Wang; Han Pang; Jing Liu

doi:10.1016/j.jcis.2023.04.095

Amorphous dominated metal hydroxide-organic framework with compositional and structural heterogeneity for enhancing anodic electro-oxidation reactions

J Colloid Interface Sci. 2023 Aug 15:644:358-367. doi: 10.1016/j.jcis.2023.04.095. Epub 2023 Apr 25.

Authors

Wenjun Tang¹, Zebin Yu², Honglei Chen¹, Ronghua Jiang³, Jun Huang⁴, Shuang Li⁵, Yanping Hou¹, Mi Wang¹, Han Pang¹, Jing Liu¹

Affiliations

¹ State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, School of Resources, Environment and Materials, Guangxi University, Nanning 530004, PR China.
² State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, School of Resources, Environment and Materials, Guangxi University, Nanning 530004, PR China. Electronic address: xxzx7514@hotmail.com.
³ School of Chemical and Environmental Engineering, Shaoguan University, Shaoguan 512005, PR China.
⁴ College of Civil Engineering & Architecture, Guangxi University, Nanning 530004, PR China.
⁵ School of Environmental Science and Technology, Dalian University of Technology, Dalian 116023, PR China.

PMID: 37120884
DOI: 10.1016/j.jcis.2023.04.095

Abstract

Inorganic-organic hybrids are promising anode catalysts to realize high activity and stability. Herein, an amorphous-dominated transition metal hydroxide-organic framework (MHOF) with isostructural mixed-linker was successfully synthesized on nickel foam (NF) substrate. The designed IML₂₄-MHOF/NF exhibited remarkable electrocatalytic activity with an ultralow overpotential of 271 mV for oxygen evolution reaction (OER) and a potential of 1.29 V vs. reversible hydrogen electrode for urea oxidation reaction (UOR) at 10 mA·cm^-2. Furthermore, the IML₂₄-MHOF/NF||Pt-C cell required only 1.31 V for urea electrolysis at 10 mA·cm^-2, which was much smaller than traditional water splitting (1.50 V). When coupled with UOR, the hydrogen yield rate was faster (1.04 mmol·h^-1) than with OER (0.32 mmol·h^-1) at 1.6 V. The structure characterizations, together with operando monitoring, including operando Raman, Fourier transform infrared, electrochemical impedance spectroscopy, and alcohol molecules probe, revealed that: (1) amorphous IML₂₄-MHOF/NF prefers self-adaptive reconstruction into active intermediate species against the external stimulus; (2) pyridine-3,5-dicarboxylate-incorporation into parent framework reconfigures electronic structure of system, thus mediating the absorption of oxygen-containing reactants during anodic oxidation reactions, such as O* and COO*. This work provides a new approach for boosting the catalytic activity of anodic electro-oxidation reactions by trimming the structure of MHOF-based catalysts.

Keywords: Amorphous metal hydroxide-organic framework; Kinetics of oxygen evolution reaction; Operando monitoring; Optimize adsorption of OH*; Urea oxidation reaction.