Research Progress on Transition Metal⁃Based Catalysts for Hydrogen Evolution Reaction via Seawater Electrolysis

doi:10.19894/j.issn.1000-0518.210386

Chinese Journal of Applied Chemistry ›› 2022, Vol. 39 ›› Issue (6): 927-940.DOI: 10.19894/j.issn.1000-0518.210386

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Research Progress on Transition Metal⁃Based Catalysts for Hydrogen Evolution Reaction via Seawater Electrolysis

Yan WANG, Shu-Cong ZHANG, Xing-Kun WANG, Zhi-Cheng LIU, Huan-Lei WANG, Ming-Hua HUANG()

School of Materials Science and Engineering，Ocean University of China，Qingdao 266100，China

Received:2021-07-31 Accepted:2021-11-23 Published:2022-06-01 Online:2022-06-27
Contact: Ming-Hua HUANG
About author:huangminghua@ouc.edu.cn
Supported by:
the National Natural Science Foundation of China(21775142);the Natural Science Foundation of Shandong Province(ZR2020ZD10)

Abstract

Abstract:

As one of the most abundant natural resources on earth， seawater has unique advantages in realizing large-scale hydrogen production from electrochemical water splitting. However， the catalysts at the cathode could be corroded， poisoned or degraded by Cl^－， Ca²⁺ and Mg²⁺ in seawater， resulting in a significant reduction in their activity and stability. Therefore， the development of cheap， efficient and stable electrocatalysts for hydrogen evolution reaction （HER） on the cathode has attracted intense attention. This review firstly elaborates the major advantages and challenges for hydrogen production from seawater electrolysis. Afterwards， the research progress on transition metal-based HER catalysts for seawater electrolysis， such as selenides， sulfides， phosphates， nitrides and so on， is summarized and discussed. Finally， the future perspectives in the design of efficient and stable HER catalysts for seawater electrolysis are summarized and put forward.

Key words: Seawater, Electrocatalysis, Hydrogen evolution reaction, Transition metal-based catalysts

CLC Number:

O646.5

Yan WANG, Shu-Cong ZHANG, Xing-Kun WANG, Zhi-Cheng LIU, Huan-Lei WANG, Ming-Hua HUANG. Research Progress on Transition Metal⁃Based Catalysts for Hydrogen Evolution Reaction via Seawater Electrolysis[J]. Chinese Journal of Applied Chemistry, 2022, 39(6): 927-940.

Figures/Tables 6

Fig.1 （a） HER polarization curves of Ni-Mo-S/C the molar ratio of Ni to Mo is 1∶1 in seawater. Inset： photograph of gas bubbles formed on the catalyst surface during the test［40］； HRTEM images of （b） Co-Se1 and （c） Co-Se4. Inset： SEM and elemental distribution mapping of （b） Co-Se1 and （c） Co-Se4；（d） Polarization curves of Co-Se1||Co-Se4 and Ir-C||Pt-C for overall water splitting in buffer solution （pH=7.4） and natural seawater［36］；（e） HER and （f） OER polarization curves of the Fe，P-NiSe2 NFs in 0.5 mol/L KOH + Seawater， 1.0 mol/L KOH and natural seawater［41］

Fig.2 （a） HER polarization curves of Mo5N6 in seawater；（b） Chronoamperometric curve of Mo5N6 under an applied potential of 310 mV；（c） Comparison of current retention of Mo5N6 and commercial Pt/C after 4 h stability test［22］；（d） Polarization curves of NiNS||NiNS and Ir-C||Pt-C for overall water splitting in 1.0 mol/L KOH， buffer solution （pH=7.4） and seawater；（e-f） HRTEM images of NiNS［45］；（g） HER polarization curves of h-MoN@BNCNT and commercial 20% Pt/C in seawater； Inset： the corresponding Tafel plots；（h） HER polarization curves after the 100th CV cycles tests and （i） Chronoamperometric curves of h-MoN@BNCNT and commercial 20% Pt/C catalysts［46］

Fig.3 （a） Schematic illustration for the synthesis of porous cobalt phosphide electrocatalyst；（b） HER polarization curves of C300P350， C400P350 and C500P350 electrocatalysts obtained at different calcination temperatures in simulated seawater；（c） Chronopotentiometric curve of C400P350 at 50 mA/cm2 ［51］；（d） HER polarization curves of Fe-Co2P BNRs and commercial Pt/C in seawater［52］；（e） Schematic illustration for the synthesis of porous featherlike NiCoP electrocatalyst supported by nickel foam （NiCoP/NF）；（f） HER polarization curves of NiCoP/NF in natural seawater［53］；（g） HER polarization curves of CoMoP@C， commercial Pt/C （20% and 40%） catalysts after the 5th， 10th and 20th CV cycles tests［54］

Fig.4 （a） HER and （b） OER polarization curves of Ni2P-Fe2P/NF in 1.0 mol/L KOH+Seawater；（c） Chronopotentiometric curves of Ni2P-Fe2P/NF at the current densities of 100 and 500 mA/cm2［55］；（d） Schematic illustration for the synthesis of Ni5P4@Ni2+δ O δ （OH）2-δ hybrid nanosheets （NPNNS）；（e） HER polarization curves of NPNNS and commercial Pt/C in natural seawater （pH=7.8）［56］；（f） Schematic illustration for the synthesis of sandwich-like nanostructured NiCoN|Ni x P|NiCoN；（g） HER polarization curves，（h） overpotential at the current density of 10 mA/cm2 of NiCoN|Ni x P|NiCoN catalysts in natural seawater， and （i） Chronopotentiometric curves at the constant current density of 10 mA/cm2 ［25］

Fig.5 （a） HER polarization curve of the Co3Mo3C/CNT modified Ni foam electrode in seawater；（b） HER polarization curves before and after 5000 CV cycles tests in seawater， Inset：Chronoamperometric curve at an overpotential of 170 mV［59］；（c） HER polarization curves of Mo2C-MoP NPC/CFP-800 and commercial Pt/C in seawater；（d） Chronoamperometric curve of Mo2C-MoP NPC/CFP-800 under a static overpotential of 385 mV［64］；（e） HER polarization curves of VS2@V2C and commercial Pt/C in seawater after the 2th， 5th， 10th， 20th and 50th CV cycles tests；（f） Chronoamperometric curves of VS2@V2C with loading of 0.1， 0.2 and 0.4 mg/cm2［65］；（g） HER polarization curves after the 1 th， and 5 th CV cycles tests and （h） Chronoamperometric curves at an overpotential of 500 mV for Co0.31Mo1.69C/MXene/NC and commercial Pt/C in natural seawater［66］

Table 1 The HER performance of transition metal?based catalysts in seawater

催化剂 Catalysts	过电势η₁₀（下角标表示电流密度为10 mA/cm²，特别标注除外）/mV η₁₀（the subscript denotes i= 10 mA/cm²， unless otherwise specified）/mV	电解液 Electrolyte	稳定性 Stability test/h	Tafel 斜率Tafel slope/ （mV·dec^-1）	参考文献Ref.
Ni?Mo?S/C	~460	天然海水 Natural seawater	-	-	［40］
MoS₂QD?aerogel?100	~370	天然海水 Natural seawater	-	-	［67］
Co?Se4	330	缓冲海水 Buffered seawater	-	-	［36］
Fe， P?NiSe₂ NFs	η₅₀≈320	天然海水 Natural seawater	200	-	［41］
Mo₅N₆	257	天然海水 Natural seawater	100@310 mV	-	［22］
Ni?SA/NC	139	碱性天然海水 1.0 mol/L KOH+Seawater	14@200 mV	123	［71］
Ni?SN@C	23	碱性天然海水 1.0 mol/L KOH+Seawater	40@25 mV	41	［72］
NiMoN	η₁₀₀ =339	碱性模拟海水 1.0 mol/L KOH+0.5 mol/L NaCl	-	-	［27］
NiNS	197	天然海水 Natural seawater	-	-	［45］
Ni₃N@C/NF	η₁₀₀ =142	碱性天然海水 1.0 mol/L KOH+Seawater	100@100 mA/cm²	-	［69］
h? MoN@BNCNT	~160	天然海水 Natural seawater	16	128	［46］
C400P350	454	模拟海水 Simulated seawater	24@10 mA/cm²	107	［51］
Fe?Co₂P BNRs	489	天然海水 Natural seawater	100@40 mA/cm²	-	［52］
PF?NiCoP/NF	287	天然海水 Natural seawater	20@290 mV	-	［53］
CoMoP@C	448	天然海水 Natural seawater	10@500 mV	-	［54］
CoNiP/Co _x P	290	天然海水 Natural seawater	500@10 mA/cm²	-	［70］
Ni₂P?Fe₂P	η₁₀₀=252	碱性天然海水 1.0 mol/L KOH+Seawater	36@100 mA/cm²	-	［55］
NPNNS	144	天然海水 Natural seawater	40	108	［56］
NiCoN\|Ni _x P\|NiCoN	165	天然海水 Natural seawater	24@10 mA/cm²	139.2	［25］

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Research Progress on Transition Metal⁃Based Catalysts for Hydrogen Evolution Reaction via Seawater Electrolysis

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