journal article·2024-08-22Open access

Bimetallic Ni–Mn Electrocatalysts for Stable Oxygen Evolution Reaction in Simulated/Alkaline Seawater and Overall Performance in the Splitting of Alkaline Seawater

Sukomol Barua, Aldona Balčiūnaitė, Daina Upskuvienė, Jūrate Vaičiūnienė, Loreta Tamašauskaitė-Tamašiūnaitė, Eugenijus Norkus

Coatings· Volume 14· Issue 8

Abstract

The perfect strategy for the generation of green and renewable hydrogen (H2) fuels is the direct electrocatalytic splitting of plentiful seawater rather than scarce freshwater. One of the half-reactions taking place during the electrocatalytic splitting of seawater is oxygen evolution (OER). However, the OER is affected by slow four-electron transfer kinetics as well as competitive chlorine evolution reactions (CERs) in seawater. To overcome the kinematic and competitive barriers of seawater splitting and achieve an excellent overall performance of seawater splitting, we herein report a facile, low-cost, one-step fabrication procedure of 3D structured nickel–manganese (NiMn) coatings using a dynamic hydrogen bubble template (DHBT) technique. The electrocatalytic activities of the thus synthesized catalytic materials for OER in simulated seawater (0.5 M NaCl + 1 M KOH, denoted as SSW) and alkaline natural seawater (natural seawater + 1 M KOH, denoted as ASW) were investigated using linear sweep voltammetry (LSV) at varying temperatures from 25 to 75 °C. Scanning electron microscopy (SEM) and inductively coupled plasma–optical emission spectroscopy (ICP–OES) were used to examine the surface morphology and composition of the prepared catalysts. It was found that the prepared NiMn/Ti-1 catalyst in a plating bath containing a molar ratio of 1:1 Ni2+:Mn2+ and having the lowest Mn loading of 13.43 µg cm−2 exhibited quite reasonable activity for OER in Cl− ion rich SSW and ASW. To achieve the benchmark current density of 10 mA cm−2 in SSW and ASW, the NiMn/Ti-1 electrocatalyst requires overpotentials of 386 and 388 mV, respectively. In addition, this optimal bimetallic electrocatalyst also demonstrated superior long-run stability at 1.81 V (vs. RHE) and 10 mA cm−2 for 24 h in both working electrolytes. Impressively, the two-electrode electrolyzer—NiMn/Ti-5(−)||NiMn/Ti-1(+)—needs only 1.619 V to deliver 10 mA cm−2 current density for overall alkaline seawater electrolysis, which is even 0.075 V lower than the noble metal-based electrolyzer (Pt(−)||NiMn/Ti-1(+)).
Source: crossref · Quality: baseline

Research context

OpenAlex topics: Electrocatalysts for Energy Conversion · Electrochemical Analysis and Applications · Fuel Cells and Related Materials

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Catalysis, Center for Physical Sciences and Technology (FTMC), LT-10257 Vilnius, Lithuania

References (100+)

Show source-provided references
1. Clean and affordable hydrogen fuel from alkaline water splitting: Past, recent progress, and future prospects10.1002/adma.202007100 ↗
2. Perfecting electrocatalysts via imperfections: Towards the large-scale deployment of water electrolysis technology10.1039/D0EE03635H ↗
3. Current understanding and challenges of solar-driven hydrogen generation using polymeric photocatalysts10.1038/s41560-019-0456-5 ↗
4. Hydrogen power gets a boost10.1126/science.ade8092 ↗
5. Overview of the next quarter century vision of hydrogen fuel cell electric vehicles10.1016/j.ijhydene.2018.10.112 ↗
6. Electrochemical water splitting: Bridging the gaps between fundamental research and industrial applications10.1002/eem2.12441 ↗
7. Hydrogen energy future: Advancements in storage technologies and implications for sustainability10.1016/j.est.2023.108404 ↗
8. Direct seawater electrolysis by adjusting the local reaction environment of a catalyst
9. Advances, opportunities, and challenges of hydrogen and oxygen production from seawater electrolysis: An electrocatalysis perspective10.1016/j.coelec.2021.100879 ↗
10. Synergizing aliovalent doping and interface in heterostructured NiV nitride@oxyhydroxide core-shell nanosheet arrays enables efficient oxygen evolution10.1016/j.nanoen.2021.105961 ↗
11. Nanostructured metallic FeNi2S4 with reconstruction to generate FeNi-based oxide as a highly-efficient oxygen evolution electrocatalyst10.1016/j.nanoen.2020.105619 ↗
12. Lithiation-Induced Defect Engineering to Promote Oxygen Evolution Reaction10.1002/adfm.202209753 ↗
13. Mechanisms of the oxygen evolution reaction on NiFe2O4 and CoFe2O4 Inverse-Spinel Oxides10.1021/acscatal.2c01534 ↗
14. Advances in hydrogen production from electrocatalytic seawater splitting10.1039/D1NR00784J ↗
15. Direct electrolytic splitting of seawater: Opportunities and challenges10.1021/acsenergylett.9b00220 ↗
16. Recent advances in electrocatalysts for seawater splitting10.1016/j.nanoms.2020.12.003 ↗
17. Strategies of designing electrocatalysts for seawater splitting10.1016/j.jssc.2021.122799 ↗
18. Rational design of core-shell-structured CoPx@FeOOH for efficient seawater electrolysis10.1016/j.apcatb.2021.120256 ↗
19. Challenges and opportunities for seawater electrolysis: A mini-review on advanced materials in chlorine-involved electrochemistry
20. Electrolysis of low-grade and saline surface water10.1038/s41560-020-0550-8 ↗
21. Design criteria, operating conditions, and nickel–iron hydroxide catalyst materials for selective seawater electrolysis10.1002/cssc.201501581 ↗
22. Jiang, S., Liu, Y., Qiu, H., Su, C., and Shao, Z. (2022). High selectivity electrocatalysts for oxygen evolution reaction and anti-chlorine corrosion strategies in seawater splitting. Catalysts, 12.10.3390/catal12030261 ↗
23. Emerging porous solids for electrocatalytic and photocatalytic seawater splitting10.1016/j.ccr.2024.215935 ↗
24. Non-precious-metal catalysts for alkaline water electrolysis: Operando characterizations, theoretical calculations, and recent advances10.1039/D0CS00575D ↗
25. Low-PGM and PGM-free catalysts for proton exchange membrane fuel cells: Stability challenges and material solutions10.1002/adma.201908232 ↗
26. Iridium-incorporated Co3O4 with lattice expansion for energy-efficient green hydrogen production coupled with glycerol valorization10.1039/D2CC06931H ↗
27. Advances in noble metal (Ru, Rh, and Ir) doping for boosting water splitting electrocatalysis10.1039/D1TA01108A ↗
28. Rhodium nanocrystals on porous graphdiyne for electrocatalytic hydrogen evolution from saline water10.1038/s41467-022-32937-2 ↗
29. Ni-based heterostructure with protective phosphide layer to enhance the oxygen evolution reaction for the seawater electrolysis10.1016/j.ijhydene.2023.07.282 ↗
30. Boosting oxygen evolution in seawater media at large current density via boron-doped (Ni, Fe) OOH grown on Ni3N nanosheets10.1016/j.apcatb.2024.123871 ↗
31. A highly efficient and long-term durable electrocatalyst for oxygen evolution in alkaline seawater by growing Ni1.5Fe1.5B on the NiMoO4 nanorods10.1016/j.mtchem.2023.101849 ↗
32. Hierarchical Ni@CNTs-bridged MoxC/Ni2P heterostructure micro-pillars for enhanced seawater splitting and Mg/seawater battery10.1016/j.nanoen.2023.108440 ↗
33. Corrosion resistance and earth-abundance FeS-based heterojunction catalyst for seawater splitting at industrial grade density10.1016/j.jcis.2023.12.001 ↗
34. Nanoneedles like FeP engineered on Ni-foam as an effective catalyst towards overall alkaline freshwater, urea, and seawater splitting10.1016/j.fuel.2024.131725 ↗
35. Constructing the Fe/Cr double (oxy) hydroxides on Fe3O4 for boosting the electrochemical oxygen evolution in alkaline seawater and domestic sewage10.1016/j.apcatb.2021.120847 ↗
36. Robust and efficient iron-based electrodes for hydrogen production from seawater at high current density above 1000 mA cm−210.1016/j.cej.2024.151705 ↗
37. In situ growth of volcano-like FeIr alloy on nickel foam as efficient bifunctional catalyst for overall water splitting at high current density10.1016/j.cej.2021.129892 ↗
38. Engineering heterostructured and hierarchical CoP/CoFeP nanosheet for effective oxygen evolution reaction in alkaline freshwater and seawater10.1016/j.ijhydene.2024.05.342 ↗
39. Self-assembled heterojunction CoSe2@CoO catalysts for efficient seawater electrolysis10.1016/j.electacta.2023.142870 ↗
40. Near surface electric field enhancement: Pyridinic-N rich few-layer graphene encapsulating cobalt catalysts as highly active and stable bifunctional ORR/OER catalyst for seawater batteries10.1016/j.apcatb.2022.121361 ↗
41. Phosphorus coordinated Co/Se2 heterointerface nanowires: In-situ catalyst reconstruction towards efficient overall water splitting in alkaline and seawater media10.1016/j.jallcom.2023.172240 ↗
42. Cobalt chromium vanadium layered triple hydroxides as an efficient oxygen electrocatalyst for alkaline seawater splitting10.1039/D1CC05745F ↗
43. Nitrogen doped FeCoNiS nanoparticles on N, S-co-doped vertical graphene as bifunctional electrocatalyst for water splitting10.1016/j.ijhydene.2022.10.216 ↗
44. Multi-shelled CoS2–MoS2 hollow spheres as efficient bifunctional electrocatalysts for overall water splitting10.1016/j.ijhydene.2020.03.045 ↗
45. Understanding the sulphur-oxygen exchange process of metal sulphides prior to oxygen evolution reaction10.1038/s41467-023-37751-y ↗
46. Pei, Z., Qin, T., Tian, R., Ou, Y., and Guo, X. (2023). Construction of an amethyst-like MoS2@Ni9S8/Co3S4 rod electrocatalyst for overall water splitting. Nanomaterials, 13.10.3390/nano13162302 ↗
47. Porous transition metal phosphides derived from Fe-based Prussian blue analogue for oxygen evolution reaction10.1016/j.jallcom.2019.152332 ↗
48. Controllable synthesis of crystal-amorphous heterostructures in transition metal phosphide and enhancement mechanism for overall water splitting10.1016/j.apsusc.2023.158961 ↗
49. Controlled synthesis of M (M = Cr, Cu, Zn and Fe)-NiCoP hybrid materials as environmentally friendly catalyst for seawater splitting10.1016/j.jallcom.2023.171516 ↗
50. DFT-assisted rational design of CoMxP/CC (M = Fe, Mn, and Ni) as efficient electrocatalyst for wide pH range hydrogen evolution and oxygen evolution10.1007/s12274-022-4771-y ↗
51. Hetero-interfacial nickel nitride/vanadium oxynitride porous nanosheets as trifunctional electrodes for HER, OER and sodium ion batteries10.1016/j.jechem.2023.01.064 ↗
52. Recycling valuable cobalt from spent lithium ion batteries for controllably designing a novel sea-urchin-like cobalt nitride-graphene hybrid catalyst: Towards efficient overall water splitting10.1016/j.jechem.2021.03.052 ↗
53. 2D porous Co-Mo nitride heterostructures nanosheets for highly effective electrochemical water splitting10.1016/j.apsusc.2023.156989 ↗
54. Iron-doped cobalt nitride as an efficient electrocatalyst towards energy saving hydrazine assisted seawater splitting in near neutral to highly alkaline pH achieving industry level current density10.1016/j.ijhydene.2023.10.299 ↗
55. Low-cost high entropy alloy (HEA) for high-efficiency oxygen evolution reaction (OER)10.1007/s12274-021-3802-4 ↗
56. High entropy alloy nanoparticles as efficient catalysts for alkaline overall seawater splitting and Zn-air batteries10.1016/j.jcis.2023.05.074 ↗
57. Hierarchical CoNi2S4@NiMn-layered double hydroxide heterostructure nanoarrays on superhydrophilic carbon cloth for enhanced overall water splitting10.1016/j.electacta.2020.136247 ↗
58. Nano-NiFe LDH assembled on CNTs by electrostatic action as an efficient and durable electrocatalyst for oxygen evolution10.1016/j.jelechem.2023.117718 ↗
59. Iron doped cobalt nickel layered double hydroxide supported on nickel foam as a robust electrocatalyst for highly efficient water oxidation in alkaline sea water10.1016/j.electacta.2023.143269 ↗
60. Spherical Ni3S2/Fe-NiPx Magic Cube with Ultrahigh Water/Seawater Oxidation Efficiency10.1002/advs.202104846 ↗
61. Interface engineering of hierarchical branched Mo-doped Ni3S2/NixPy hollow heterostructure nanorods for efficient overall water splitting10.1002/aenm.201903891 ↗
62. Promoting nickel oxidation state transitions in single-layer NiFeB hydroxide nanosheets for efficient oxygen evolution10.1038/s41467-022-33846-0 ↗
63. Morphology evolution regulation of dual-doped S, Fe-NiMoO4 microrods based on precipitation-dissolution equilibrium for oxygen evolution10.1016/j.fuel.2022.126769 ↗
64. Surface-oxidized iron–cobalt–nickel alloy with continuous variable composition for hydrogen and oxygen evolution reaction10.1021/acssuschemeng.2c04892 ↗
65. Self-supported hierarchical porous FeNiCo-based amorphous alloys as high-efficiency bifunctional electrocatalysts towards overall water splitting10.1016/j.ijhydene.2021.08.223 ↗
66. Enhanced electrocatalysis of NiMnIn Heusler alloy films for hydrogen evolution reaction by magnetic field10.1016/j.jallcom.2021.160271 ↗
67. Electrodeposition of Ni-Fe-Mn ternary nanosheets as affordable and efficient electrocatalyst for both hydrogen and oxygen evolution reactions10.1016/j.ijhydene.2020.06.249 ↗
68. Bimetallic MnNi-hydroxide electrodeposited on Ni-foam for superior water-splitting and energy storage10.1016/j.ijhydene.2023.10.208 ↗
69. The rise of manganese as catalysts for acidic water oxidation: A mini review10.1016/j.elecom.2023.107505 ↗
70. Pulse electrodeposited FeCoNiMnW high entropy alloys as efficient and stable bifunctional electrocatalysts for acidic water splitting10.1016/j.cej.2022.137452 ↗
71. Interfacial construction and lattice distortion-triggered bifunctionality of Mn-NiS/Mn-Ni3S4 for H2 production10.1016/j.fuel.2022.125337 ↗
72. Deep eutectic solvent mediated synthesis of Mn-based hybrid electrocatalyst for oxygen evolution reaction: Insights into the effect of anion on the evolution of structure-activity10.1016/j.apsusc.2023.158843 ↗
73. Efficient energy-saving hydrogen production on binder-free electrodeposited hierarchical Ni-Mn-P@Ni-Co nanostructure10.1016/j.ijhydene.2023.10.310 ↗
74. Enhancing OER activity of Ni/Co oxides via Fe/Mn substitution within tailored mesoporous frameworks10.1021/acsaem.2c02055 ↗
75. Facile electrodeposition of Mn-CoP nanosheets on Ni foam as high-rate and ultrastable electrodes for supercapacitors
76. Synthesis of nest-like porous MnCo-P electrocatalyst by electrodeposition on nickel foam for hydrogen evolution reaction10.1016/j.ijhydene.2021.12.011 ↗
77. Ni-Mn based alloys as versatile catalysts for different electrochemical reactions10.1016/j.jpowsour.2014.06.145 ↗
78. Electrodeposited CrMnFeCoNi Oxy-carbide film and effect of selective dissolution of Cr on oxygen evolution reaction10.1016/j.jmst.2024.02.068 ↗
79. Mn-Co bimetallic phosphate on electrodeposited PANI nanowires with composition modulated structural morphology for efficient electrocatalytic water splitting10.1016/j.apcatb.2021.120202 ↗
80. Mn-doped nickel-copper phosphides as oxygen evolution reaction electrocatalyst in alkaline seawater solution10.1016/j.ijhydene.2024.05.094 ↗
81. Fe, Mn-Ni3S2 directly grown on nickel foam as an environmentally friendly electrocatalyst for seawater splitting10.1016/j.surfin.2024.104079 ↗
82. Barua, S., Balčiūnaitė, A., Vaičiūnienė, J., Tamašauskaitė-Tamašiūnaitė, L., and Norkus, E. (2023). Bimetallic 3D nickel-manganese/titanium bifunctional electrocatalysts for efficient hydrogen and oxygen evolution reaction in alkaline and acidic media. Coatings, 13.10.3390/coatings13061102 ↗
83. Three-dimensional heterostructured NiCoP@NiMn-layered double hydroxide arrays supported on Ni foam as a bifunctional electrocatalyst for overall water splitting10.1021/acsami.9b15208 ↗
84. Double functionalization of Mo2C and NiMn-LDH assembling g-C3N4 as efficient bifunctional electrocatalysts for selective electrocatalytic reactions and overall water splitting10.1002/er.8006 ↗
85. Interface engineering of heterogeneous NiMn layered double hydroxide/vertically aligned NiCo2S4 nanosheet as highly efficient hybrid electrocatalyst for overall seawater splitting10.1016/j.chemosphere.2023.141016 ↗
86. Precision and correctness in the evaluation of electrocatalytic water splitting: Revisiting activity parameters with a critical assessment10.1039/C7EE03457A ↗
87. Comparison of electrochemical active surface area methods for various nickel nanostructures10.1016/j.jelechem.2020.114246 ↗
88. Zabielaite, A., Balciunaite, A., Upskuviene, D., Simkunaite, D., Levinas, R., Niaura, G., Vaiciuniene, J., Jasulaitiene, V., Tamasauskaite-Tamasiunaite, L., and Norkus, E. (2023). Investigation of hydrogen and oxygen evolution on cobalt-nanoparticles-supported graphitic carbon nitride. Materials, 16.10.3390/ma16175923 ↗
89. Nickel and manganese oxide heterostructure nanoparticles supported by carbon nanotube for highly efficient oxygen evolution reaction catalysis10.1016/j.apsusc.2021.151699 ↗
90. ZIF67-derived Co-CoO@C nanocomposites as highly efficient and selective oxygen evolution reaction (OER) catalysts for seawater electrolysis10.1016/j.ijhydene.2023.09.122 ↗
91. Ultrafast synthesis of Cu2O octahedrons inlaid in Ni foam for efficient alkaline water/seawater electrolysis10.1016/j.elecom.2021.107177 ↗
92. Modulating the electronic structure on cobalt sites by compatible heterojunction fabrication for greatly improved overall water/seawater electrolysis10.1021/acssuschemeng.2c02571 ↗
93. Electrolytic splitting of saline water: Durable nickel oxide anode for selective oxygen evolution10.1016/j.ijhydene.2019.01.120 ↗
94. Synergistic action of Co-Fe layered double hydroxide electrocatalyst and multiple ions of sea salt for efficient seawater oxidation at near-neutral pH10.1016/j.electacta.2017.08.098 ↗
95. Selective seawater splitting using pyrochlore electrocatalyst10.1021/acsaem.0c00383 ↗
96. Strong-proton-adsorption Co-based electrocatalysts achieve active and stable neutral seawater splitting10.1002/adma.202210057 ↗
97. Iron phosphate modified calcium iron oxide as an efficient and robust catalyst in electrocatalyzing oxygen evolution from seawater10.1039/C8FD00172C ↗
98. Structural buffer engineering on metal oxide for long-term stable seawater splitting10.1002/adfm.202201127 ↗
99. Constructing high-activity cobalt-based perovskite hybrid by a top-down phase evolution method for the direct seawater electrolysis anode10.1016/j.jallcom.2022.165342 ↗
100. 3D Nickel-manganese bimetallic electrocatalysts for an enhanced hydrogen evolution reaction performance in simulated seawater/alkaline natural seawater10.1016/j.ijhydene.2024.07.131 ↗