In Situ Ammonium Formation Mediates Efficient Hydrogen Production from Natural Seawater Splitting

Overview

Journal Nat Commun

Specialty Biology

Date 2024 Nov 2

PMID 39487190

Authors

Xiao-Long Zhang

Peng-Cheng Yu

Shu-Ping Sun

Lei Shi

Peng-Peng Yang

Zhi-Zheng Wu

Li-Ping Chi

Ya-Rong Zheng

Min-Rui Gao

Affiliations

Soon will be listed here.

Abstract

Seawater electrolysis using renewable electricity offers an attractive route to sustainable hydrogen production, but the sluggish electrode kinetics and poor durability are two major challenges. We report a molybdenum nitride (MoN) catalyst for the hydrogen evolution reaction with activity comparable to commercial platinum on carbon (Pt/C) catalyst in natural seawater. The catalyst operates more than 1000 hours of continuous testing at 100 mA cm without degradation, whereas massive precipitate (mainly magnesium hydroxide) forms on the Pt/C counterpart after 36 hours of operation at 10 mA cm. Our investigation reveals that ammonium groups generate in situ at the catalyst surface, which not only improve the connectivity of hydrogen-bond networks but also suppress the local pH increase, enabling the enhanced performances. Moreover, a zero-gap membrane flow electrolyser assembled by this catalyst exhibits a current density of 1 A cm at 1.87 V and 60 C in simulated seawater and runs steadily over 900 hours.

Citing Articles

Comprehensive Chlorine Suppression: Advances in Materials and System Technologies for Direct Seawater Electrolysis.

Zhao C, Ding Z, Zhang K, Du Z, Fang H, Chen L Nanomicro Lett. 2025; 17(1):113.

PMID: 39841341 PMC: 11754585. DOI: 10.1007/s40820-025-01653-z.

References

Wang N, Ou P, Hung S, Huang J, Ozden A, Abed J . Strong-Proton-Adsorption Co-Based Electrocatalysts Achieve Active and Stable Neutral Seawater Splitting. Adv Mater. 2023; 35(16):e2210057. DOI: 10.1002/adma.202210057. View

Jin H, Xu J, Liu H, Shen H, Yu H, Jaroniec M . Emerging materials and technologies for electrocatalytic seawater splitting. Sci Adv. 2023; 9(42):eadi7755. PMC: 10584342. DOI: 10.1126/sciadv.adi7755. View

Serva A, Scalfi L, Rotenberg B, Salanne M . Effect of the metallicity on the capacitance of gold-aqueous sodium chloride interfaces. J Chem Phys. 2021; 155(4):044703. DOI: 10.1063/5.0060316. View

Liu H, Li J, Qin X, Ma C, Wang W, Xu K . Pt-O synergistic sites on MoO/γ-MoN heterostructure for low-temperature reverse water-gas shift reaction. Nat Commun. 2022; 13(1):5800. PMC: 9530113. DOI: 10.1038/s41467-022-33308-7. View

Zhang X, Hu S, Wang Y, Shi L, Yang Y, Gao M . Plasma-Assisted Synthesis of Metal Nitrides for an Efficient Platinum-Group-Metal-Free Anion-Exchange-Membrane Fuel Cell. Nano Lett. 2022; 23(1):107-115. DOI: 10.1021/acs.nanolett.2c03707. View

Liu H, Shen W, Jin H, Xu J, Xi P, Dong J . High-Performance Alkaline Seawater Electrolysis with Anomalous Chloride Promoted Oxygen Evolution Reaction. Angew Chem Int Ed Engl. 2023; 62(46):e202311674. DOI: 10.1002/anie.202311674. View

Ros C, Murcia-Lopez S, Garcia X, Rosado M, Arbiol J, Llorca J . Facing Seawater Splitting Challenges by Regeneration with Ni-Mo-Fe Bifunctional Electrocatalyst for Hydrogen and Oxygen Evolution. ChemSusChem. 2021; 14(14):2872-2881. DOI: 10.1002/cssc.202100194. View

Alexander A, Hargreaves J . Alternative catalytic materials: carbides, nitrides, phosphides and amorphous boron alloys. Chem Soc Rev. 2010; 39(11):4388-401. DOI: 10.1039/b916787k. View

McCrory C, Jung S, Peters J, Jaramillo T . Benchmarking heterogeneous electrocatalysts for the oxygen evolution reaction. J Am Chem Soc. 2013; 135(45):16977-87. DOI: 10.1021/ja407115p. View

10.

Alfarano S, Pezzotti S, Stein C, Lin Z, Sebastiani F, Funke S . Stripping away ion hydration shells in electrical double-layer formation: Water networks matter. Proc Natl Acad Sci U S A. 2021; 118(47). PMC: 8617503. DOI: 10.1073/pnas.2108568118. View

11.

Chatenet M, Pollet B, Dekel D, Dionigi F, Deseure J, Millet P . Water electrolysis: from textbook knowledge to the latest scientific strategies and industrial developments. Chem Soc Rev. 2022; 51(11):4583-4762. PMC: 9332215. DOI: 10.1039/d0cs01079k. View

12.

Kuang Y, Kenney M, Meng Y, Hung W, Liu Y, Huang J . Solar-driven, highly sustained splitting of seawater into hydrogen and oxygen fuels. Proc Natl Acad Sci U S A. 2019; 116(14):6624-6629. PMC: 6452679. DOI: 10.1073/pnas.1900556116. View

13.

Liu E, Li J, Jiao L, Doan H, Liu Z, Zhao Z . Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts. J Am Chem Soc. 2019; 141(7):3232-3239. DOI: 10.1021/jacs.8b13228. View

14.

Kresse , Hafner . Ab initio molecular dynamics for liquid metals. Phys Rev B Condens Matter. 1993; 47(1):558-561. DOI: 10.1103/physrevb.47.558. View

15.

Lv C, Qian Y, Yan C, Ding Y, Liu Y, Chen G . Defect Engineering Metal-Free Polymeric Carbon Nitride Electrocatalyst for Effective Nitrogen Fixation under Ambient Conditions. Angew Chem Int Ed Engl. 2018; 57(32):10246-10250. DOI: 10.1002/anie.201806386. View

16.

Shi Z, Li J, Jiang J, Wang Y, Wang X, Li Y . Enhanced Acidic Water Oxidation by Dynamic Migration of Oxygen Species at the Ir/Nb O Catalyst/Support Interfaces. Angew Chem Int Ed Engl. 2022; 61(52):e202212341. DOI: 10.1002/anie.202212341. View

17.

Chong L, Gao G, Wen J, Li H, Xu H, Green Z . La- and Mn-doped cobalt spinel oxygen evolution catalyst for proton exchange membrane electrolysis. Science. 2023; 380(6645):609-616. DOI: 10.1126/science.ade1499. View

18.

Xu W, Wang Z, Liu P, Tang X, Zhang S, Chen H . Ag Nanoparticle-Induced Surface Chloride Immobilization Strategy Enables Stable Seawater Electrolysis. Adv Mater. 2023; 36(2):e2306062. DOI: 10.1002/adma.202306062. View

19.

Li J, Hu J, Zhang M, Gou W, Zhang S, Chen Z . A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution. Nat Commun. 2021; 12(1):3502. PMC: 8190308. DOI: 10.1038/s41467-021-23750-4. View

20.

de Lima G, Duarte H, Pliego Jr J . Dynamical discrete/continuum linear response shells theory of solvation: convergence test for NH4+ and OH- ions in water solution using DFT and DFTB methods. J Phys Chem B. 2010; 114(48):15941-7. DOI: 10.1021/jp110202e. View