An overview and recent advances in electrocatalysts for direct seawater splitting

doi:10.1007/s11705-021-2102-6

Front. Chem. Sci. Eng.

2021, Vol. 15

Issue (6) : 1408-1426 https://doi.org/10.1007/s11705-021-2102-6

REVIEW ARTICLE

An overview and recent advances in electrocatalysts for direct seawater splitting

Hao-Yu Wang, Chen-Chen Weng, Jin-Tao Ren, Zhong-Yong Yuan(

)

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), School of Materials Science and Engineering, Nankai University, Tianjin 300350, China

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Abstract

In comparison to pure water, seawater is widely accepted as an unlimited resource. The direct seawater splitting is economical and eco-friendly, but the key challenges in seawater, especially the chlorine-related competing reactions at the anode, seriously hamper its practical application. The development of earth-abundant electrocatalysts toward direct seawater splitting has emerged as a promising strategy. Highly efficient electrocatalysts with improved selectivity and stability are of significance in preventing the interference of side reactions and resisting various impurities. This review first discusses the macroscopic understanding of direct seawater electrolysis and then focuses on the strategies for rational design of electrocatalysts toward direct seawater splitting. The perspectives of improved electrocatalysts to solve emerging challenges and further development of direct seawater splitting are also provided.

Keywords seawater splitting electrocatalysts oxygen evolution reaction hydrogen evolution reaction chlorine chemistry

Corresponding Author(s): Zhong-Yong Yuan

Online First Date: 22 October 2021 Issue Date: 09 November 2021

Cite this article:

Hao-Yu Wang,Chen-Chen Weng,Jin-Tao Ren, et al. An overview and recent advances in electrocatalysts for direct seawater splitting[J]. Front. Chem. Sci. Eng., 2021, 15(6): 1408-1426.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-021-2102-6
https://academic.hep.com.cn/fcse/EN/Y2021/V15/I6/1408

Fig.1 Illustrations for the mechanisms of OER vs. chloride chemistry. (a) The Pourbaix diagram of an artificial model solution (0.5 mol·L^–1 NaCl solution with electrolytes to control the pH and no other chlorine species) depicting the thermodynamic equilibrium of H₂O/O₂ (green line) and Cl^–/Cl₂-HOCl-OCl^– (red line). Reprinted with permission from ref. [24], copyright 2016, Wiley-VCH. Free energy diagram over RuO₂ (110) for (b) ClER Volmer-Heyrovsky mechanism and (c) two OER competing water splitting reactions (electrochemical and chemical pathway) at different potentials. Reprinted with permission from ref. [25], copyright 2018, American Chemical Society. (d) ΔG_loss volcano diagram for OER (black) and chloride evolution reaction (ClER, gray). Reprinted with permission from ref. [26], copyright 2014, Wiley-VCH.

Catalyst	Support	Electrolyte	Prominent performance	Ref.
(MnMo)O_x	IrO₂/Ti	0.5 mol·L^–1 NaCl	OER selectivity of 91%	[36]
(Mn-W)O_x	IrO₂/Ti	0.5 mol·L^–1 NaCl	OER selectivity of 99.6%	[37]
Co₃O₄	Ni foam	1 mol·L^–1 KOH+ natural seawater	Overpotential: about 280 mV for HER and 450 mV for OER at 100 mA·cm^–2	[38]
Co-Fe-O-B	Glassy carbon	1 mol·L^–1 KOH+ 0.5 mol·L^–1 NaCl	Overpotential: 294 mV for OER at 10 mA·cm^–2	[39]
(Mn_0.88Mo_0.12)O_2.12	IrO₂/Ti	0.5 mol·L^–1 NaCl	OER selectivity of 99.6% after 1500 h electrolysis at 100 mA·cm^–2	[40]
NiFe-LDH	Membrane	0.5 mol·L^–1 KOH+ 0.5 mol·L^–1 NaCl	Stable electrolysis at 200 mA·cm^–2 for 100 h	[41]
S-(Ni,Fe)OOH	Ni foam	1 mol·L^–1 KOH+ natural seawater	Overpotential of 300 and 398 mV for OER at 100 and 500 mA·cm^–2	[42]
NiCoS	Ni foam	1 mol·L^–1 KOH+ natural seawater	Stable electrolysis at 800 mA·cm^–2	[43]
RuO₂:Zn	Ti mesh	150 mmol·L^–1 NaCl+ 0.1 mol·L^–1 HClO₄	Change of selectivity by the incorporation of Zn	[44]
Pb2Ru2O7−_x	Glassy carbon	0.1 mol·L^–1 NaOH+ 0.6 mol·L^–1 NaCl	OER selectivity of 99% at pH= 13 and 5 h stable electrolysis at 200 mA·cm^–2	[45]
Co-Se4	Co foil	Buffered seawater (pH= 7.09)	10.3 mA·cm^–2 at 1.8 V for overall seawater electrolysis	[46]
Co-Pi	Glassy carbon	0.5 mol·L^–1 NaCl+ 0.1 mol·L^–1 Pi (pH= 7.0)	Retained activity for O₂ generation in Cl^–-containing electrolyte	[47]
Co/Co₃O₄@C	Carbon fiber paper	1 mol·L^–1 KOH+ natural seawater	Overpotential: about 600 mV for HER and 630 mV for OER at 10 mA·cm^–2	[48]
Co-Fe LDH	Ti mesh	Simulated seawater (pH= 8.0)	Stable electrolysis for a diurnal cycle (8 h·d^–1)	[49]
MnO_x/IrO_x	Glassy carbon	30 mmol·L^–1 KCl+ 0.5 mol·L^–1 KHSO₄	CER selectivity decreased from 86% to 7% by MnO_x deposition	[50]
CaFeO_x\|FePO₄	FTO	Buffered synthetic seawater (pH= 7.0)	Overpotential: about 710 mV for OER at 10 mA·cm^–2 and stable electrolysis for over 10 h	[51]
GO@Fe@Ni-Co	Ni foam	1 mol·L^–1 KOH+ 0.5 mol·L^–1 NaCl	20 and 1000 mA·cm^–2 at 1.57 and 2.02 V for overall seawater electrolysis	[52]
NM/IrO₂	Ti mesh	0.5 mol·L^–1 NaCl (pH= 8.3)	OER selectivity of nearly 100% by Nafion coating	[53]
NiFe/NiS_x	Ni foam	1 mol·L^–1 KOH+ 0.5 mol·L^–1 NaCl	Stable electrolysis at 1000 mA·cm^–2 for over 500 h	[54]

Tab.1 Oxygen evolution electrocatalysts reported in saline electrolyte

Fig.2 Maximum allowed overpotential region where only OER is thermodynamically possible in seawater electrolysis. The E–E_OER values are the difference between chloride-related reactions (chlorine evolution, hypochlorous acid formation and hypochlorite formation reaction) and OER at different pH values. Reprinted with permission from ref. [24], copyright 2016, Wiley-VCH.

Fig.3 Polarization curves for the (a) S-(NiFe)OOH and (b) NiCoS electrode tested in different electrolytes. Reprinted with permission from ref. [42], copyright 2020, Royal Society of Chemistry and ref. [43], copyright 2021, Elsevier, respectively.

Fig.4 (a) Original current density (black) and current densities attributed to oxygen (black) and chlorine (red) for anodic OER in 0.1 mol·L^–1 HClO₄ + 0.14 mol·L^–1 NaCl solution. Reprinted with permission from ref. [44], copyright 2010, Wiley-VCH. (b) OER current efficiencies at various potentials for PbRu₂O₇ and RuO₂ in 0.6 mol·L^–1 NaCl. Reprinted with permission from ref. [45], copyright 2020, American Chemical Society. (c) Polarization curves of Co-Se1//Co-Se4 and Ir-C//Pt-C in buffer solution and seawater. Reprinted from with permission ref. [46], copyright 2018, Wiley-VCH.

Fig.5 (a) Sketch of OER and ClER on IrO_x/GC catalyst with and without MnO_x deposition. Reprinted with permission from ref. [50], copyright 2018, American Chemical Society. (b) Representation of the improved selectivity and stability on active NiFeO_x catalyst with CeO_x deposition. Reprinted with permission from ref. [62], copyright 2018, Wiley-VCH. (c) Schematic illustration of the preparation of GO@Fe@Ni-Co@NF. Reprinted with permission from ref [52], copyright 2020, Royal Society of Chemistry.

Fig.6 (a) Reduction potential-dependent sequential reduction of platinum group metal (PGM) in Ni-Mo matrix; (b) hydrogen evolution polarization curves of Pt/C and Pt/Ni-Mo; (c) the comparison of the Pt/Ni-Mo and other PGM-based and Non-PGM catalysts. Reprinted with permission from ref. [63], copyright 2021, Wiley-VCH.

Fig.7 Schematic illustration of the preparation of nitrogen-deficient 2D MoN and nitrogen 2D Mo₅N₆ electrocatalysts through an ammonization synthesis without and with Ni-induced process, respectively. Reprinted with permission from ref. [73], copyright 2018, American Chemical Society.

Fig.8 Schematic illustration of the preparation of (a) CoMoP@C catalyst and (b) U-CNT-900 catalyst. Reprinted with permission from ref. [77], copyright 2017, Royal Society of Chemistry and ref. [33], copyright 2015, Royal Society of Chemistry.

Fig.9 (a) Schemes for AEMWE using asymmetric feeding electrolyte with different electrolyte composition. Reprinted with permission from ref. [98], copyright 2020, Royal Society of Chemistry. (b) Scheme of a GO device for concentration-cell measurements, hydrogen pumping and water vapor electrolysis. Reprinted with permission from ref. [100], copyright 2018, American Chemical Society.

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