Recent Trends in Transition Metal Phosphide (TMP)-Based Seawater Electrolysis for Hydrogen Evolution
Abstract
:1. Introduction
2. A synopsis of TMPs
Structure: Fundamental Concepts
3. Electrolysis of Seawater
3.1. Characteristics of Seawater Catalytic Reaction
3.2. Complementary Effects of Complex Ions
3.3. Effects of Complex Ions
4. Seawater Challenge and Perspectives
5. Seawater Electrolysis with TMP-Based Catalysts
5.1. Dopants
5.2. Structure of Bimetal Phosphide Phases
5.3. Compounds of TMPs
6. Conclusions and Outlook
- i.
- After more evaluation, TMPs can be anticipated to be an essential tool for the hydrogen energy sector. Since oxidation products can considerably damage and even ruin TMP-based catalyst activity and durability, seawater electrolysis without CER is more advantageous.
- ii.
- More research must be conducted to determine the exact mechanism(s) underlying TMP-based catalysts. Furthermore, one of the remaining barriers to the commercial viability of TMPs and multi-elemental TMPs as catalysts is the development of a scalable, cost-effective synthesis methodology.
- iii.
- It is exceedingly important to develop catalysts that are more selective for HER and OER than other competing reactions.
- iv.
- Even though TMPs have sophisticated chemical and physical features, their ability to catalyze is inadequate as a result of their poor electrical conductivity and the high absorption energies of the hydrogen intermediates.
- v.
- Despite significant progress in explaining the OER and HER electrocatalytic methodologies, several issues remain in the direction of commercial large-scale hydrogen production via seawater splitting by electrolysis.
- vi.
- Consequently, it is anticipated that electronic structure modulation, microstructure regulation, and multi-component hybrid engineering will be helpful resources for designing effective TMP-based HER electrocatalysts.
- vii.
- TMP-based HER electrocatalysts can now compete with exceptionally advanced noble metal catalysts. We, therefore, compared common electrocatalysts made using the aforementioned multiscale strategies from the standpoint of HER catalytic activity and stability.
- viii.
- TMP-based catalysts should also benefit from being inexpensive and simple to prepare in order to ensure their wide-scale commercial application.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
Nomenclature
References
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Type | Characteristics | References |
---|---|---|
Phosphides (TMPs) | The metal and P sites in TMPs function as hydride acceptors and proton acceptor centers. Metal phosphides exhibit excellent electrical conductivity when the right quantities and ratios of metal and phosphorus atoms are used. TMPs can also be produced by the use of elemental phosphorus at temperatures above 600 °C. TMPs demonstrated substantial activity and stability in seawater electrolysis. The electrochemical stability was greatly improved by the synergistic contribution of 3D pore structures, electronic effects, and conductive substrates. | [17,19,20,21] |
Oxides (TMOs) | TMOs are regarded as effective HER catalysts due to their diverse crystal structures, resources, and significant catalytic activity, which may lead to Pt-like performance in HER. The amorphous structure offers more active sites for electrocatalytic reactions. | [22] |
The structure of metal oxide materials influences electrocatalytic performance as well. The amorphous material’s atom arrangement can result in a large number of exposed surfaces and defects. Due to their low activity and poor conductivity, they perform poorly when compared with comparable electrocatalysts. Defect engineering is a more promising approach for improving HER performance by making the edge sites available. It has been exploited by many researchers in diverse research fields, such as photocatalytic materials, rational design of NH3 semiconductor photocatalysts, and developments in SERS material design based on semiconductors. It can also be used to enhance the catalytic performance of 2D TMOs (e.g., 2D CeO2) | [23,24,25,26,27] | |
Dihalides (TMDs) | Can outperform other noble metal catalysts due to their high degree of chemical stability and adaptability across a wide range of pH values. The HER activity of TMDs can be increased by doping with both metallic atoms (e.g., Fe, Co, Ni) and non-metallic atoms (e.g., B, N, O), according to experiments and DFT calculations. They have great potential in ECR applications. | [28,29,30] |
Carbides (TMCs) | The disordered structure, which provides a significant number of uncharged sulfur atoms as active sites for HER and a quasiperiodic arrangement of nanodomains for fast interdomain electron transport, is attributed to the excellent HER electrocatalytic activity (e.g., commercial Mo2C in both acid/basic media). Aside from their high electrical conductivity, their properties of H2 adsorption and d-band electronic density state (similar to Pt) show an optimal combination, which is thought to be the main factor for the observed high HER activity. | [31,32] |
Nitrite (TMNs) | Very good at conducting electricity and resisting corrosion. Stable for seawater splitting. The vast majority of bulk TMNs that have been reported have HER activity that is listed below expectations due to a lack of hydrogen bonding energy. | [33,34,35] |
Method of TMPs Synthesis | Advantages | Disadvantages | References |
---|---|---|---|
Metal Organic Framework (MOF)-derived methods | Control of morphology High surface area Composition control Doped carbon layer formation | Two steps with lab-scale synthesis methods | [45] |
Wet chemical methods | Monodispersed particles Composition control Single-step methods | Difficult to control the reaction conditions as highly volatile solvent required | |
Bulk conversion | Large-scale synthesis Composition control | Bulk microstructure Poisonous byproduct gas formation | |
Phytic acid-derived methods | Large-scale synthesis Composition control Doped carbon layer formation | Microstructure optimization |
Catalysts | Forms | Outcomes | References |
---|---|---|---|
Binary phosphides | |||
CoP | Nanotube, nanoparticles, nanosheets, nanorods | Improved catalyst activity and stability through the synergetic effect of the bimetal. Has a rounded shape after phosphorization. | [51,52] |
Co2P | Nanoflowers, nanoparticles, nanosheets | Enhanced electrochemical performance. Highly active HER electrocatalyst. High redox reactivity in an alkaline system. | [53,54] |
Cu3P | Nanoarrays, nanowires | Much higher surface roughness and exposes more active sites. Acted as an energy-efficient, bifunctional catalyst electrode with high activity. | [55,56] |
MoP | Nanoflakes, nanoparticles | The resulting electrode worked as an active catalyst for both OER and HER in an alkaline electrolyte. Contributes significantly to the high activity of the catalyst. | [57,58] |
Ternary phosphides | |||
NiCo2Px | Nanowires | Interesting morphologies and catalytic performance may reveal long-term stability in all pH conditions. Exhibited impressive universal pH catalytic performance. | [59,60] |
Ni–Fe–P | Nanocubes | At 350 °C, the catalyst displayed a distinctive porous nanocube morphology with a loose and uneven surface. It demonstrated excellent HER and OER activities as well as exceptional long-term stability. Exposed a greater number of active sites and ensured adequate contact between catalyst and electrolyte. | [68] |
CoMoP NiCu-P | Core-shell, Porous | With a Faradaic efficiency (FE) of 92.5%, it demonstrated superior stability and HER performance in real seawater. The carbon shell’s high proton ability to absorb effectively raises HER performance. | [64] |
NaH2PO2, TOP, Red P | Plethora of P sources | The electrode showed outstanding electrochemical stability, regardless of electrolyte pH, and high HER activity in a wide pH range. | [61,62,63] |
Supported phosphides | |||
Alumina, silica | Alumina, silica | Al2O3 has a high water content of 30%, which causes the intrinsic oxidation of the metal and P in the TMPs. | [67] |
Activated carbon | Activated carbon | Presence of micropores with poor mechanical stability. It can be modified through the electric potential to remove biogas such as HeS. | [65,66,69] |
MCM-41, SBA-15 | Mesoporous silica | High surface area and acid site density. | [70] |
Magnesium (Mg2+) | Chloride (Cl−) | Sodium (Na+) | Sulfate (SO42−) | Calcium (Ca2+) | Total Dissolved Salts (TDS) |
---|---|---|---|---|---|
1295 | 19,345 | 10,752 | 2710 | 416 | 35,000 |
New Technologies | Description | Efficiency (%) | References |
---|---|---|---|
Membrane electrolyzer | Up to a particular length, two distinct laminar flow streams can be kept apart, ensuring the formation of an imaginary layer separating the anode and cathode. | 40–80 | [91,92,93,94] |
Unutilized regenerative technology | Reversible electrolyzer and FC combined, able to produce power and hydrogen (a tiny dimension available). | 43–51 | [91,95,96] |
Battolyser technology | After being fully charged, batteries can produce hydrogen. | 76–90 | [91,94,97,98] |
Anion exchange membrane (AEM) | Membrane that is semipermeable to anions but impermeable to gases like oxygen (O2) or hydrogen (H2). | 67–74 | [91,99,100,101,102] |
Catalyst | Tafel Slope (mV dec−1) | Overpotential @10 mA cm−2 (mV) | Electrolytes | Electrodes | References |
---|---|---|---|---|---|
Co(OH)2 | 125 | - | Mg(ClO4)2 | FTO | [85] |
Co(OH)2 | 63 | - | MgCl2 | FTO | [85] |
Mg|Co- MnO2/Co(OH)2 | 151 | - | 0.25 M Mg(ClO4)2 | FTO | [85] |
Mg|Co MnO2/Co(OH)2 | 144 | - | 0.25 M MgCl2 | FTO | [85] |
NiFe-LDH | - | 227 (100 mA/cm2) | 1 M KOH + 0.5 M NaCl | NF | [130] |
S-(Ni,Fe)OOH | - | 300 (100 mA/cm2) | 1 M KOH + Seawater | NF | [131] |
S-(Ni,Fe)OOH | 48.9 | 281 (100 mA/cm2) | 1 M KOH | NF | [131] |
FTO/NiO | - | 401 | 1.0 M KOH + 0.5 M NaCl | FTO | [132] |
Pb2Ru2O7−x | 48 | 500 | 0.6 M NaCl | GCE | [133] |
Pb2Ru2O7−x | 45 | 200 | 0.6 M NaCl + 0.1 M NaOH | GCE | [133] |
Ti@NiB | 34.2 | 397 (50 mA/cm2) | 1 M KOH + 0.5 M NaCl | Ti plate | [134] |
Co-Fe-O-B | - | 294 | 1 M KOH + 0.5 M NaCl | GCE | [135] |
multilayered NiFeBx | - | 263 ± 14 | 1 M KOH + 0.5 M NaCl | - | [136] |
NiMoN@NiFeN | - | 369 (500 mA/cm2) | 1 M KOH + Seawater | NF | [106] |
Fe-Ni(OH)2/Ni3S2 | 46 | 269 | 1 M KOH + 0.5 M NaCl | NF | [137] |
Catalyst | Tafel Slope (mV dec−1) | Overpotential @10 mA cm−2 (mV) | Electrolytes | Electrodes | References |
---|---|---|---|---|---|
VS2@V2C | 37 | 148 (20 mA cm−2) | seawater (PH = 0) | GCE | [138] |
h-MoN@BNCNT | 128 | - | seawater | GCE | [139] |
NiCoP/NF | - | 287 | Seawater artificial | NF | [105] |
PSS-PPy/Ni-Co-P | - | 144 | Seawater | CF | [140] |
C-Co2P | - | 30 | 1 M KOH, 1 M KOH, 0.5 M NaCl, 41.2 × 10−3 | GCE | [141] |
C-Co2P | - | 192 (1000 mA cm−2) | M MgCl2 and 12.5 × 10−3 M CaCl | GCE | [141] |
Ru-CoOx | - | 630 (100 mA cm−2) | 1 M KOH + Seawater | NF | [142] |
Mo5N6 | - | 94 | 1.0 M KOH | GCE | [35] |
Ni-SN@C | - | 28 | 1 M KOH | GCE | [143] |
Ni-SN@C | - | 23 | 1 M KOH Seawater | GCE | [143] |
NiCoN|NixP|NiCoN | - | 165 | Seawater | NF | [88] |
Ni5P4/Ni2+δOδ(OH)2-δ | - | 144 | Seawater | CC | [47] |
Pt-Ru-Cr | 45.7 | 256 | Seawater | Ti mesh | [144] |
Pt | 45.8 | 285 | Seawater | Ti mesh | [144] |
Pt-Ru-Fe | 46 | 248 | Seawater | Ti mesh | [144] |
Pt-Ru-Co | 44.8 | 222 | Seawater | Ti mesh | [144] |
Pt-Ru-Ni | 44.5 | 206 | Seawater | Ti mesh | [144] |
Pt-Ru-Mo | 44.0 | 196 | Seawater | Ti mesh | [144] |
Pt/C | 59 | - | Seawater | GCE | [145] |
PtNi5 | 119 | - | Seawater | GCE | [145] |
Pt-Ru-Cr0.1 | - | 283.8 | Seawater | Ti mesh | [146] |
Pt-Ru-Fe0.1 | - | 275.2 | Seawater | Ti mesh | [146] |
Pt-Ru-Co0.1 | - | 266.5 | Seawater | Ti mesh | [146] |
Pt-Ru-Ni0.1 | - | 263.3 | Seawater | Ti mesh | [146] |
Pt-Ru-Mo0.1 | - | 254.6 | Seawater | Ti mesh | [146] |
Ti/NiPt | 111 | - | Seawater | Ti foil | [147] |
Ti/NiAu | 170 | - | Seawater | Ti foil | [147] |
Ru/Co | 107 | - | Seawater | Ti foil | [76] |
Ru/Mo1 | 137 | - | Seawater | Ti foil | [76] |
0.5 Rh-G1000 | - | 340 | Seawater | GCE | [148] |
Pt@mh-3D MXene | - | 280 | Seawater | GCE | [149] |
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Tahri, W.; Zhou, X.; Khan, R.; Sajid, M. Recent Trends in Transition Metal Phosphide (TMP)-Based Seawater Electrolysis for Hydrogen Evolution. Sustainability 2023, 15, 14389. https://doi.org/10.3390/su151914389
Tahri W, Zhou X, Khan R, Sajid M. Recent Trends in Transition Metal Phosphide (TMP)-Based Seawater Electrolysis for Hydrogen Evolution. Sustainability. 2023; 15(19):14389. https://doi.org/10.3390/su151914389
Chicago/Turabian StyleTahri, Walid, Xu Zhou, Rashid Khan, and Muhammad Sajid. 2023. "Recent Trends in Transition Metal Phosphide (TMP)-Based Seawater Electrolysis for Hydrogen Evolution" Sustainability 15, no. 19: 14389. https://doi.org/10.3390/su151914389