Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

doi:10.1007/s40820-024-01382-9

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Abstract

Metal-organic frameworks (MOFs) have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity, but the limited catalytic activity and stability has hampered their practical use in water splitting. Herein, we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs (donated as AE-CoNDA) to serve as efficient catalyst for water splitting. AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm⁻² and a small Tafel slope of 62 mV dec⁻¹ with excellent stability over 100 h. After integrated AE-CoNDA onto BiVO₄, photocurrent density of 4.3 mA cm⁻² is achieved at 1.23 V. Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p, which accounts for the fast kinetics and high activity. Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.

Key words： Metal-organic frameworks Bond length adjustment Spin state transition Orbitals hybridization Water splitting

Received: 17 December 2023 Published: 19 April 2024

Corresponding Authors: Yang Hou

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	Fan He
	Yingnan Liu
	Xiaoxuan Yang
	Yaqi Chen
	Cheng-Chieh Yang
	Chung-Li Dong
	Qinggang He
	Bin Yang
	Zhongjian Li
	Yongbo Kuang
	Lecheng Lei
	Liming Dai
	Yang Hou

Cite this article:

Fan He,Yingnan Liu,Xiaoxuan Yang, et al. Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization[J]. Nano-Micro Letters, 2024, 16(1): 175-.

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https://www.qk.sjtu.edu.cn/nml/EN/10.1007/s40820-024-01382-9 OR https://www.qk.sjtu.edu.cn/nml/EN/Y2024/V16/I1/175

Fig. 1 PEC-OER performances of AE-CoNDA@BiVO4. a Schematic diagram of working principle of a proposed PEC-OER cell. b Polarization curves of BiVO4, CoNDA@BiVO4, and AE-CoNDA@BiVO4 without adding sacrificial agent (Na2SO3) under chopped AM 1.5G irradiation. c IPCE curves and d ABPE curves of BiVO4, CoNDA@BiVO4, and AE-CoNDA@BiVO4 under AM 1.5G irradiation. e Stability of AE-CoNDA@BiVO4 under AM 1.5G irradiation at 2.5 mA cm−2, inset: amount of O2 evolution detected by gas chromatography and calculated from photocurrent during the PEC-OER of AE-CoNDA@BiVO4 at 0.6 V. f Photocurrent density at 0.6 V and 1.23 V, IPCE, ABPE, and stability of AE-CoNDA@BiVO4 compared with other reported Co-based BiVO4 photoanodes. All experiments were carried out in a 1.0 M potassium borate (pH = 9.0) solution

Fig. 2 Electrocatalytic OER performances of AE-CoNDA. a Polarization curves and b Tafel slopes of AE-CoNDA, CoNDA, and Ir/C. c Internal and external voltammetric charge density and electron porosity of CoNDA and AE-CoNDA. d TOF values and e response of Rct at different potentials for CoNDA and AE-CoNDA. f Chronopotentiometric durability of AE-CoNDA at 1.5 V

Fig. 3 Electronic structure analysis of AE-CoNDA. High-resolution a Co 2p and b O 1s spectra of CoNDA and AE-CoNDA. c Co K-edge XANES spectra of AE-CoNDA, CoNDA, and Co foil. d Co L-edge XANES spectra of AE-CoNDA, CoNDA, CoO, and Co foil

Fig. 4 Fine structure analysis and spin state transition of AE-CoNDA. a Fourier transformed EXAFS spectra of AE-CoNDA, CoNDA, and Co foil, inset: EXAFS fitting curves in R space of AE-CoNDA and CoNDA. b O K-edge XANES spectra of AE-CoNDA, CoNDA, and CoO. c Temperature-dependent inverse susceptibilities of AE-CoNDA and CoNDA by the susceptibilities derived from the magnetizations (χ = M/H) follows by Curie-Weiss law. d An illustration of 3d-orbitals of AE-CoNDA and CoNDA

Fig. 5 Investigation on correlation between spin states of AE-CoNDA with OER activity. a An illustration of AE-CoNDA during OER process including the Co active sites and oxygen-contained intermediates adsorption. Calculated spin-resolved DOS of b AE-CoNDA and c CoNDA. d Calculated charge density difference of AE-CoNDA and CoNDA. The yellow and cyan regions represent electron accumulation and depletion. e The free energy diagrams of CoNDA and AE-CoNDA of OER

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