Seawater Electrolysis Performance of Self-supported Amorphous Ce-FeHPi/NF Electrode

doi:10.15541/jim20240172

Abstract

Abstract:

To solve the existing energy crisis and achieve continuous seawater electrolysis, it is necessary to design efficient electrocatalysts to deal with the problems of slow anodic oxygen evolution and chloride ion (Cl^-) corrosion. In this study, a unique nanostructural modified Ce-FeHPi/NF electrode was prepared by a one-step hydrothermal method on a nickel foam (NF) skeleton. The experimental results show that Ce doping regulates the surface morphology of FeHPi/NF, forming amorphous nanospheres, which not only enables the catalytic layer to grow into a compact nanostructure, but also greatly increases the active surface area of the electrode, significantly improving the electrocatalytic activity. In addition, the presence of phosphoric acid group can effectively repel Cl^- on surface of the electrode, which enhances its corrosion resistance, and stabilizes it in seawater for a long time. The 10%Ce-FeHPi/NF electrode in alkaline simulated seawater (1 mol·L^-1 KOH + 0.5 mol·L^-1 NaCl) electrolyte requires only a low overpotential of 296 mV to reach a current density of 100 mA·cm^-2. In 1 mol·L^-1 KOH + 1 mol·L^-1 NaCl, the 10%Ce-FeHPi/NF electrode runs stably for more than 130 h at a constant potential of 1.774 V (vs. RHE). Therefore, the modified nanostructured material prepared in this study can effectively improve the oxygen evolution activity of electrodes, and provide a new way for the development of seawater electrolytic anode catalytic materials.

Key words: seawater electrolysis, anode material, phosphorylation compound, one-step hydrothermal

CLC Number:

TQ151

XIAO Wenyan, FU Yan, YANG Shubin, ZHU Jie, CHENG Zhaoyang, WEN Xiaoxu, TANG Jiafan, YU Liang, ZHANG Qian. Seawater Electrolysis Performance of Self-supported Amorphous Ce-FeHPi/NF Electrode[J]. Journal of Inorganic Materials, 2024, 39(12): 1348-1356.

Figures/Tables 19

Fig. 1 Preparation flow of the Ce-FeHPi/NF

Fig. 2 SEM images of (a) FeHPi/NF, (b) 5%Ce-FeHPi/NF, (c) 15%Ce-FeHPi/NF, and (d-f) 10%Ce-FeHPi/NF

Fig. 3 Nitrogen adsorption/desorption curves and pore size distributions for (a) FeHPi/NF and (b) 10%Ce-FeHPi/NF

Fig. 4 XRD patterns of FeHPi/NF and Ce-FeHPi/NF (a) Large angle analysis; (b) Magnified patterns

Fig. 5 Water contact angles (WCA) of different samples (a) NF; (b) FeHPi/NF; (c) 10%Ce-FeHPi/NF

Fig. 6 XPS spectra of FeHPi/NF and Ce-FeHPi/NF (a) Full spectra; (b) Fe2p; (c) P2p; (d) O1s; (e) Ce3d; (f) C1s

Fig. 7 (a, b) OER polarization curves, (c, d) overpotentials, and (e, f) Tafel plots of Ce-FeHPi/NF samples in different electrolytes (a, c, e) 1 mol·L-1 KOH; (b, d, f) 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl; Colorful figures are available on website

Fig. 8 Double layer capacitances of FeHPi/NF and Ce-FeHPi/NF Electrolyte: 1 mol·L-1 KOH

Fig. 9 Nyquist plots of NF, FeHPi/NF and Ce-FeHPi/NF Colorful figures are available on website

Fig. 10 I-t curves of 10%Ce-FeHPi/NF samples in different electrolytes

Table S1 Amounts of Fe, P and Ce in 10%Ce-FeHPi/NF determined by ICP-OES

Element	Weight/%
Fe	1.0341
Ce	0.2593
P	2.8334

Fig. S1 EDS spectra of 10%Ce-FeHPi/NF

Fig. S2 (a, b) OER polarization curves, (c, d) overpotentials, and (e, f) Tafel plots of electrodes in different electrolytes (a, c, e) 1 mol·L-1 KOH; (b, d, f) 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl

Fig. S3 Cyclic voltammetric curves at different scanning rates in non-Faraday reaction intervals (a) FeHPi/NF; (b) 5%Ce-FeHPi/NF; (c) 10%Ce-FeHPi/NF; (d) 15%Ce-FeHPi/NF; 1 mol·L-1 KOH

Fig. S4 LSV polarization curves normalized by Cdl

Fig. S5 (a) OER polarization curves in different electrolytes, and (b) constant current step plot of 10%Ce-FeHPi/NF in 1 mol·L-1 KOH + 0.5 mol·L-1 NaCl

Fig. S6 Residual chlorine testing for the electrolyte after the long-term stability test (1 mol·L-1 KOH + 1 mol·L-1 NaCl, E=1.774 V(vs. RHE), 130 h)

Fig. S7 Faraday efficiency test of 10%Ce-FeHPi/NF (a) Schematic diagram of testing equipment; (b) Faraday efficiency results

Fig. S8 (a-e) XPS spectra and (f) SEM image of 10%Ce-FeHPi/NF after long reaction (a) Full spectra; (b) Fe2p; (c) Ce3d; (d) P2p; (e) O1s

References 33

[1]	YANG L, LIU Z, ZHU S, et al. Ni-based layered double hydroxide catalysts for oxygen evolution reaction. Materials Today Physics, 2021, 16: 100292.
[2]	ZHOU Q, LIAO L, BIAN Q, et al. Engineering in-plane nickel phosphide heterointerfaces with interfacial sp H-P hybridization for highly efficient and durable hydrogen evolution at 2 A·cm^-2. Small, 2022, 18(4):2105642.
[3]	MO Y, LIAO L, LI D, et al. Development prospects of metal-based two-dimensional nanomaterials in lithium-sulfur batteries. Chinese Chemical Letters, 2023, 34(1):107130. DOI
[4]	AN P, YANG B, ZHANG N, et al. Hybrid TaON/LaTiO₂N photoelectrode for water oxidation. Transportation Safety and Environment, 2019, 1(3):212.
[5]	WAN X, ZHAO Y, LI Z, et al. Emerging polymeric electrospun fibers: from structural diversity to application in flexible bioelectronics and tissue engineering. Exploration, 2022, 2(1):20210029.
[6]	JIANG L L, XU S S, XIA B K, et al. Defect engineering of graphene hybrid catalysts for oxygen reduction reactions. Journal of Inorganic Materials, 2022, 37(2):215. DOI
[7]	ZHAO Z, CHENG G, ZHANG Y, et al. Metal-organic-framework based functional materials for uranium recovery: performance optimization and structure/functionality-activity relationships. ChemPlusChem, 2021, 86(8):1177. DOI PMID
[8]	TURNER J A. Sustainable hydrogen production. Science, 2004, 305(5686):972. DOI PMID
[9]	RASHID M M, AL MESFER M K, NASEEM H, et al. Hydrogen production by water electrolysis: a review of alkaline water electrolysis, PEM water electrolysis and high-temperature water electrolysis. International Journal of Engineering and Advanced Technology, 2015, 4(3):80.
[10]	STIBER S, SATA N, MORAWIETZ T, et al. A high-performance, durable and low-cost proton exchange membrane electrolyser with stainless steel components. Energy & Environmental Science, 2022, 15(1):109.
[11]	CARMO M, FRITZ D L, MERGEL J, et al. A comprehensive review on PEM water electrolysis. International Journal of Hydrogen Energy, 2013, 38(12):4901.
[12]	CHAE K J, CHOI M, AJAYI F F, et al. Mass transport through a proton exchange membrane (nafion) in microbial fuel cells. Energy & Fuels, 2008, 22(1):80.
[13]	MAURITZ K A, MOORE R B. State of understanding of nafion. Chemical Reviews, 2004, 104(10):4535. DOI PMID
[14]	LAGUNA-BERCERO M A. Recent advances in high-temperature electrolysis using solid oxide fuel cells: a review. Journal of Power Sources, 2012, 203: 4.
[15]	KUPKA J, BUDNIOK A. Electrolytic oxygen evolution on Ni- Co-P alloys. Journal of Applied Electrochemistry, 1990, 20(6):1015.
[16]	GUANG H L, ZHU S L, LIANG Y Q, et al. Highly efficient nanoporous CoBP electrocatalyst for hydrogen evolution reaction. Rare Metals, 2021, 40(5):1031.
[17]	WANG C, SHANG H, JIN L, et al. Advances in hydrogen production from electrocatalytic seawater splitting. Nanoscale, 2021, 13(17):7897.
[18]	蒋博龙, 崔艳艳, 史顺杰, 等. 双金属氮化物NiMoN析氢催化剂制备及其电解海水析氢性能的研究. 化学学报, 2022, 80(10):1394. DOI
[19]	CONG Y, CHEN X, MEI Y, et al. CeO₂ decorated bimetallic phosphide nanowire arrays for enhanced oxygen evolution reaction electrocatalysis via interface engineering. Dalton Transactions, 2022, 51(7):2923.
[20]	YANG J, WANG Y, YANG J, et al. Quench-induced surface engineering boosts alkaline freshwater and seawater oxygen evolution reaction of porous NiCo₂O₄ nanowires. Small, 2022, 18(3):2106187.
[21]	QIU Y, LI W, ZHAO W, et al. High-rate, ultralong cycle-life lithium/sulfur batteries enabled by nitrogen-doped graphene. Nano Letters, 2014, 14(8):4821. DOI PMID
[22]	UL HAQ T, MANSOUR S, HAIK Y. Electronic and structural modification of Mn₃O₄ nanosheets for selective and sustained seawater oxidation. ACS Applied Materials & Interfaces, 2022, 14(18):20443.
[23]	ZHANG L, ZHANG R, GE R, et al. Facilitating active species generation by amorphous NiFe-Bi layer formation on NiFe-LDH nanoarray for efficient electrocatalytic oxygen evolution at alkaline pH. Chemistry — A European Journal, 2017, 23(48):11499.
[24]	LI P, ZHAO S, HUANG Y, et al. Corrosion resistant multilayered electrode comprising Ni₃N nanoarray overcoated with NiFe-phytate complex for boosted oxygen evolution in seawater electrolysis. Advanced Energy Materials, 2024, 14(8):2303360.
[25]	SONG S, WANG Y, ZHOU S, et al. One-step synthesis of heterostructural MoS₂-(FeNi)₉S₈ on Ni-Fe foam synergistically boosting for efficient fresh/seawater electrolysis. ACS Applied Energy Materials, 2022, 5(2): 1810.
[26]	SONG S, WANG Y, LIU X, et al. Synthesis of Mo-doped NiFe- phosphate hollow bird-nest architecture for efficient and stable seawater electrolysis. Applied Surface Science, 2022, 604: 154588.
[27]	SUN H, SUN J, SONG Y, et al. Nickel-cobalt hydrogen phosphate on nickel nitride supported on nickel foam for alkaline seawater electrolysis. ACS Applied Materials & Interfaces, 2022, 14(19):22061.
[28]	SONG S, ZANG J, ZHOU S, et al. Self-supported amorphous nickel-iron phosphorusoxides hollow spheres on Ni-Fe foam for highly efficient overall water splitting. Electrochimica Acta, 2021, 392: 138996.
[29]	WU L, YU L, ZHANG F, et al. Heterogeneous bimetallic phosphide Ni₂P-Fe₂P as an efficient bifunctional catalyst for water/seawater splitting. Advanced Functional Materials, 2021, 31(1):2006484.
[30]	LI M, PAN X, JIANG M, et al. Interface engineering of oxygen- vacancy-rich CoP/CeO₂ heterostructure boosts oxygen evolution reaction. Chemical Engineering Journal, 2020, 395: 125160.
[31]	WANG B, XI P, SHAN C, et al. In situ growth of ceria on cerium- nitrogen-carbon as promoter for oxygen evolution reaction. Advanced Materials Interfaces, 2017, 4(13):1700272.
[32]	WANG Y, TAO S, LIN H, et al. NaBH₄ induces a high ratio of Ni³⁺/Ni²⁺ boosting OER activity of the NiFe LDH electrocatalyst. RSC Advances, 2020, 10(55):33475.
[33]	MAHALA C, DEVI SHARMA M, BASU M. Fe-doped nickel hydroxide/nickel oxyhydroxide function as an efficient catalyst for the oxygen evolution reaction. ChemElectroChem, 2019, 6(13):3488.