Alkaline Freshwater Research Articles

Unveiling Preliminary Study of the Holocene Sedimentary Environments and Biofacies in Western of Al-Hammar Marsh, Southern Part of Iraq

Biofacies and sedimentary environment analyses were conducted across three sites west of Al-Hammar Marsh. Excavations were undertaken at different depths for a comprehensive study. The initial site was probed at 9 m depth, followed by the second site at 5 m, and the third site at 9 m. Subsequent examination of these samples aimed to unveil insights into grain size, fossil contents, and their respective ecological settings. The grain size analysis revealed three distinct sediment types: silt, sandy silt, and muddy sand. Additionally, fossil assemblages hinted at three primary biofacies. The first facies represented a fresh marsh-fluvial environment identified across all three sites at different depths. Specifically, this biofacies manifested from the surface to about 200 cm in site one, 50-150 cm in site two, and 50-250 cm in site three. The second biofacies indicated a shallow marine environment at depths ranging from 250 to 550 cm in site one, 200-300 cm in site two, and 300-650 cm in site three. Lastly, the third biofacies denoted a lagoon or tidal flat environment observed at 600-900 cm depths in site one, 300-500 cm in site two, and 700-900 cm in site three. Notably, the third biofacies in site three exhibited signs of influence from alkaline freshwater, particularly in the third location at a depth of 700-800 cm. This influence was attributed to a mixture of marine and freshwater species, including; Quinqueloculina candeiana, Quinqueloculina angulta, Cubicula fluminalis, and Melanoides tuberculate. Abundant occurrences of these species were noted in the silty clay lithology of this layer.

Modulating electronic by construction WS2/WN heterostructure coupled with N-doped carbon to boost alkaline seawater hydrogen production

The development of an efficient and durable non-precious electrocatalyst for alkaline seawater electrolysis is of great significance. Herein, two-dimensional (2D) lamellar heterostructure WS2/WN was dispersed on the carbon matrix (marked as WS2/WN@CM). The obtained WS2/WN@CM catalysts demonstrate exceptional performance in the hydrogen evolution reaction (HER) in alkaline freshwater (1.0 M KOH), alkaline simulated seawater (1.0 M KOH + 0.5 M NaCl) and alkaline natural seawater (1.0 M KOH + seawater), respectively, which achieved a low overpotential (92 mV, 95 mV and 113 mV) at 10 mA cm−2 and outstanding long-term durability at 200 mA cm−2 for 100 h. The catalyst benefits from the 3D carbon skeleton, which not only effectively prevents stacking of the 2D lamellar WS2/WN to fully utilize the active material, but also provides rapid electron transport. Moreover, stress effects at WS2/WN interfaces lead to distortions of torsion angles in the WS2 lattice, thereby increasing crystal surface defects accompanied by an enhancement of electrical conductivity. Density functional theory (DFT) calculations combined with XPS evidence confirm the electronic structure reorganization of WS2/WN at interfaces, which optimizes the adsorption energy of specific intermediates. Additionally, WN captures many electrons from WS2, so the WN region favors the reduction reaction and thus enhances the HER process.

Cr-doped tri-metallic nano prism catalyst for efficient alkaline and seawater splitting

Electrochemical water splitting is one of the most promising methods for sustainable production of green hydrogen. The oxygen evolution reaction (OER) is a crucial step in the process of water splitting. However, it exhibits sluggish kinetics and requires a significant overpotential for functioning at reasonable reactionrates. The efficiency of the reaction can be enhanced by reducing the overpotential, lowering the energy barrier, and using an effective electrocatalyst. Transition metal-basedcatalysts are well studied for this purpose. Specially, nickel–cobalt (Ni-Co) based catalysts have been regarded as the best OER electrocatalysts. Therefore, several studies have been carried out to enhance the electrocatalytic efficiency of Ni-Co catalysts. While mixing other transition metals with Ni-Co is a straightforward and reliable method to improve the OER activity of Ni-Co catalysts, there is still a need for a thorough examination of the design of Ni-Co catalysts with various additional elements. Seawater electrolysis, which utilizes abundant water resources that constitute over 97% of the world’s water, is highly appealing for sustainable energy production. To achieve commercial feasibility, scientists are striving to solve challenges, such as corrosion resistance, highoverpotential, and the need for efficient and durable electrocatalysts.In this study, we fabricated a transition metal-based trimetallic catalyst (CNF), consisting of cobalt (Co), nickel (Ni), and iron (Fe). Furthermore, CNF was doped with chromium (Cr-doped CNF) and tested for the OER in alkaline freshwater and alkaline seawater. Our Cr-doped trimetallic CNF catalyst demonstrates exceptional performance in both seawater and freshwater, with overpotential of 320 mV and 280 mV at 10 mA cm−2 current density, making it a promising candidate for large-scale, sustainable hydrogen production.

Advanced multi-component FeCoCuAlMo intermetallic electrocatalysts for efficient and sustainable hydrogen evolution in alkaline freshwater and seawater

Electrolyzing seawater to produce hydrogen is a promising sustainable energy production technology. The current non-precious metal-based hydrogen evolution reaction (HER) electrocatalysts demonstrate inadequate catalytic activity and poor stability in seawater electrolyte. Therefore, developing stable and efficient non-precious metal-based HER electrocatalysts is a major challenge for achieving sustainable green energy development. This work reports a multi-component intermetallic catalyst FeCoCuAlMo prepared by arc melting and chemical dealloying methods. The electrocatalytic hydrogen evolution performance of catalysts with varying atomic ratios (FeCoCu)20(Al70Mo30)80, (FeCoCu)30(Al70Mo30)70, (FeCoCu)40(Al70Mo30)60, and (FeCoCu)50(Al70Mo30)50 in alkaline seawater and alkaline electrolyte was studied. The findings indicate that these catalysts primarily consist of AlMo3 and (Cu0.35Fe0.35Co0.3)Al, among which the dealloyed (FeCoCu)30(Al70Mo30)70 exhibits excellent catalytic activity with overpotentials of 137.54 and 116.91 mV at a current density of 100 mA/cm2 in alkaline seawater and alkaline electrolyte, respectively, outperforming most catalysts. Additionally, it demonstrated long-term stability in alkaline seawater and alkaline electrolyte for 250 and 400 h without significant decay at overpotentials of 236 mV and 276 mV, respectively. This improved performance can be attributed to the unique structure of the multi-component intermetallic compound, which provides good thermodynamic stability and synergistic effects among its constituents, thereby enhancing HER performance. Within this multi-component intermetallic compound, AlMo3 particles serve as the primary conductive medium to accelerate electron transfer, while (Cu0.35Fe0.35Co0.3)Al serves as the main active site, resulting in a stable structure that provides the catalyst with high catalytic activity and good stability. Thus, the (FeCoCu)30(Al70Mo30)70 electrocatalyst is a promising candidate for seawater electrolysis aimed at hydrogen production.

Bimetal Metaphosphate/Molybdenum Oxide Heterostructure Nanowires for Boosting Overall Freshwater/Seawater Splitting at High Current Densities.

Exploring excellent non-noble bifunctional electrocatalysts for freshwater/seawater splitting at high current densities has attracted extensive interest owing to strong anodic oxidation and severe chloride corrosion challenges. Herein, hierarchical bimetal Ni-Co metaphosphate/molybdenum oxide heterostructure nanowires (NiCoMoPO) are rationally designed and fabricated to efficiently boost oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline freshwater/seawater, where the favorable electronic structure from heterostructures, signified by X-ray absorption spectra, endows NiCoMoPO with the enhanced intrinsic activity, while its hierarchical nanowire structure and heterostructures provide abundant active sites. Additionally, the PO3 - improves the chloride-corrosion resistance and efficiently facilitates the OER kinetics verified by theoretical and experimental studies. Therefore, NiCoMoPO drives 1000mA cm-2 at low overpotentials of 467 and 442mV for OER and HER in alkaline freshwater respectively, as well as a small cell voltage of 2.135V for overall freshwater splitting with robust durability of 300h. Impressively, due to the strong corrosion resistance, at 500mA cm-2 of overall seawater splitting, NiCoMoPO maintains almost 2.096V for 1200h, indicating promising practical applications. This work sheds light on the rational design and fabrication of outstanding electrocatalysts at high current densities of seawater/freshwater splitting.

S-doped amorphous multi-metal borophosphates for efficient alkaline seawater oxidation with a high corrosion resistance

Direct seawater splitting is a promising strategy for the production of green hydrogen to address water shortage and environmental concerns. However, the primary obstacle in direct seawater splitting is directly related to the high selectivity and durability of oxygen evolution reaction (OER) electrocatalysts. In this study, we developed sulfur-doped multimetal (Ni, Fe, and Co) borophosphates (BPOs) as high-performance OER catalysts for alkalized seawater electrolytes. The incorporated sulfur atoms act as precursors to enhance the corrosion resistance, as they form negatively charged polyanionic surface layers that block the chloride ions. The best catalyst demonstrates an overpotential of 278 mV in alkaline freshwater and 292 mV in alkalized seawater electrolytes when subjected to a current density of 100 mA cm−2. The overpotential disparity between the two media was only 14 mV, suggesting that the material has substantial resistance to chloride corrosion. Furthermore, excellent electrochemical durability was attained for the sulfurized and amorphized multi-metal BPOs, highlighting their high potential as promising catalysts for seawater oxidation.

Engineering interfacial sulfur migration in transition-metal sulfide enables low overpotential for durable hydrogen evolution in seawater

Hydrogen production from seawater remains challenging due to the deactivation of the hydrogen evolution reaction (HER) electrode under high current density. To overcome the activity-stability trade-offs in transition-metal sulfides, we propose a strategy to engineer sulfur migration by constructing a nickel-cobalt sulfides heterostructure with nitrogen-doped carbon shell encapsulation (CN@NiCoS) electrocatalyst. State-of-the-art ex situ/in situ characterizations and density functional theory calculations reveal the restructuring of the CN@NiCoS interface, clearly identifying dynamic sulfur migration. The NiCoS heterostructure stimulates sulfur migration by creating sulfur vacancies at the Ni3S2-Co9S8 heterointerface, while the migrated sulfur atoms are subsequently captured by the CN shell via strong C-S bond, preventing sulfide dissolution into alkaline electrolyte. Remarkably, the dynamically formed sulfur-doped CN shell and sulfur vacancies pairing sites significantly enhances HER activity by altering the d-band center near Fermi level, resulting in a low overpotential of 4.6 and 8 mV at 10 mA cm−2 in alkaline freshwater and seawater media, and long-term stability up to 1000 h. This work thus provides a guidance for the design of high-performance HER electrocatalyst by engineering interfacial atomic migration.

Dual Doping of B and Fe Activated Lattice Oxygen Participation for Enhanced Oxygen Evolution Reaction Activity in Alkaline Freshwater and Seawater

AbstractThe exploitation of highly activity oxygen evolution reaction (OER) electrocatalysts is critical for the application of electrocatalytic water splitting. Triggering the lattice oxygen mechanism (LOM) is expected to provide a promising pathway to overcome the sluggish OER kinetics, however, effectively enhancing the involvement of lattice oxygen remains challenging. In this study, the fabrication of B, Fe co‐doped CoP (B, Fe─CoP) nanofibers is reported, which serve as highly efficient OER electrocatalyst through phosphorization and boronation treatment of Fe‐doped Co3O4 nanofibers. Experimental results combined with theoretical calculations reveal that simultaneous incorporation of both B and Fe can more effectively trigger the participation of lattice oxygen in CoFe oxyhydroxides reconstructed from B, Fe─CoP nanofibers compared to incorporating only B or Fe. Therefore, the optimized B, Fe─CoP nanofibers exhibit superb OER activity with low overpotentials of 361 and 376 mV at 1000 mA cm−2 in alkaline freshwater and alkaline natural seawater, respectively. The present work provides significant guidelines and innovative design concepts for the development of OER electrocatalysts following the LOM pathway.

Superhydrophilic NiFe-LDH@Co9S8-Ni3S2/NF heterostructures for high-current-density freshwater/seawater oxidation electrocatalysts

Designing oxygen evolution reaction (OER) electrocatalysts with high efficiency and stability at large current densities is paramount for achieving hydrogen production through water splitting. In this study, a heterostructured NiFe-LDH coating Co9S8-Ni3S2 grown on nickel foam (NiFe-LDH@Co9S8-Ni3S2/NF) was successfully synthesized. The distinctive hierarchical structures featuring abundant heterointerfaces can effectively expose abundant active sites. The synergistic effect and strong electronic interaction between Co9S8-Ni3S2 and NiFe-LDH can enhance the intrinsic OER activity. Furthermore, the superhydrophilic characteristic of NiFe-LDH@Co9S8-Ni3S2/NF favors close contact between the electrode and electrolyte. Due to these advantages, NiFe-LDH@Co9S8-Ni3S2/NF can provide distinguished OER activity with low overpotentials of 274 mV in alkaline freshwater and 298 mV in alkaline seawater at 1000 mA cm−2, along with outstanding stability at high current density of 500 mA cm−2 over 200 h in both solutions. This study offers a valuable insight into fabricating high-performance OER electrocatalysts for seawater electrolysis in industrial applications.

Nanoneedles like FeP engineered on Ni-Foam as an effective catalyst towards overall alkaline freshwater, urea, and seawater splitting

The slow kinetics of electrochemical urea and water oxidation processes at electrode surfaces, which can be recognised as promising resources for pollution-free hydrogen energy production, motivate the scientific community to design and fabricate low-cost, high-efficiency electrocatalysts. Because the performance of electrocatalysts is dependent on their structural, morphological, and electronic properties, herein, the tuning of these properties of Fe3O4@Ni-Foam via phosphorylation and sulfurization, yielding iron phosphide (FeP@Ni-Foam) and iron sulphide (FeS@Ni-Foam), with nanoneedles (along with microstructures) and nanoflower-like morphologies, respectively, is investigated. Among all the prepared samples, FeP is found to be the most effective electrocatalyst for the oxygen evolution process (OER), the urea oxidation reaction (UOR), and seawater electrolysis. The overpotentials observed for OER, UOR, and seawater splitting are significantly reduced when using FeP as compared to other materials, with values of 207 mV, 133 mV, and 287.1 mV, respectively, at a current density of 10 mA/cm2. The enhanced catalytic activity of FeP over FeS and Fe3O4 is attributed to morphological changes, improved electronic conductivity, and exceptional endurance. The theoretical studies reveal that FeP has a better density of states over the fermi level than FeS and Fe3O4, lowering the energy barriers for the OER and UOR processes and demonstrating significant catalytic activity towards these processes. This work demonstrates that phosphorylation and sulfurization treatments can alter morphologies and electrical characteristics, hence improving the catalytic activity of the materials.

Tuning d–p Orbital Hybridization of NiMoO4@Mo15Se19/NiSe2 Core‐Shell Nanomaterials via Asymmetric Coordination Interaction Enables the Water Oxidation Process

AbstractThe electrocatalytic performance of MoNi‐based nanomaterials undergo selenization has garnered significant interest due to their modified electronic structure, while still posses certain challenges for obtained bimetallic selenides. Here, a novel MoNi‐based electrocatalyst of NiMoO4@Mo15Se19/NiSe2 core‐shell nanomaterials is constructed to promote the desorption of OOH* which can facilitate the water oxidation process. NiMoO4@Mo15Se19/NiSe2 core‐shell nanoarrays show that the “cores” are mainly NiMoO4 nanorods while the “shells” are the bimetallic selenides nanoflakes, which are super architectures that can expand more active sites and accelerate the electron transfer. Moreover, the hybridization interaction between Ni 3d, Mo 4d, and Se 4p orbitals leads to an asymmetric distribution of electric clouds, which decreases the adsorption energy and transformation of oxygen‐containing species. Electrochemical data displays that the overpotentials of NiMoO4@Mo15Se19/NiSe2 core‐shell nanomaterials are only 195 mV, 220 mV, and 224 mV for oxygen evolution reaction (OER) in alkaline freshwater, alkaline simulated seawater, and alkaline natural seawater. The current density decay is negligible after 100 h stability at about 1.46 V with a three‐electrode system in alkaline natural seawater. The low cost and the unique MoNi‐based bimetallic selenides in this work provide a more constructive solution for designing efficient and stable OER catalysts in the future.

Moderately Reconstructed Ternary Metal Nitride Nanoparticles for Highly Efficient and Robust Freshwater and Seawater Oxidation under Industrial Current Density

Transition metal nitrides (TMNs) electrocatalysts experience rapid performance degradation during oxygen evolution reaction (OER) due to severe and irreversible electrochemical reconstruction, impeding their practical application in electrochemical water splitting. To address this issue, ternary metal (Ni, Fe, Cr) nitride nanoparticles on spongy nitrogen‐doped disordered carbon skeleton electrocatalyst (NFCN/C) is synthesized using a novel one‐pot pyrolysis of eutectic mixture method. The ionomer‐free NFCN/C electrode, which undergoes moderate electrochemical reconstruction, demonstrates high OER performance in both alkaline freshwater and seawater solutions, achieving a current density of 250 mA cm−2 with low overpotentials of 349 and 364 mV, respectively. The NFCN/C anode with Pt/C cathode delivers 10 mA cm−2 at a low cell voltage of 1.49 V and exhibits long‐term durability of 450 h at 500 mA cm−2. In situ Raman spectroscopy and ultraviolet photoelectron spectroscopy (UPS), along with pre‐ and post‐characterizations, elucidate that both high electrocatalytic activity and robustness of NFCN/C for OER stem from the proposed intrinsic strategy integrating physical and electronic structures. This work paves the way for designing highly efficient and robust TMNs electrocatalysts with moderate electrochemical reconstruction for industrial freshwater and seawater electrolysis.

Anionic phosphorous and sulfur regulate self-supported Ni-Fe-based electrocatalyst for water-splitting under large current density

Nickel-iron based (Ni-Fe) catalysts are widely used in the electrolysis of water due to their high activity and low cost. However, the development of highly active non-precious metal catalysts is still a great challenge. Herein, self-supported nickel–iron phosphide is fabricated through a sulfurization/phosphorization approach (Ni-Fe-P-S-1/Ni-Fe-P-S-2). The prepared catalysts show excellent catalytic performance and stability. The HER performance of Ni-Fe-P-S-1 reaches 500 mA cm−2 with small overpotentials of 289 mV in alkaline freshwater. Meanwhile, the Ni-Fe-P-S-2 requires 312 and 375 mV to reach 500 mA cm−2 in alkaline freshwater and alkaline seawater for OER. Remarkably, at the current density of 500 mA cm−2, the Ni-Fe-P-S-1||Ni-Fe-P-S-2 electrolyzer requires only 1.85 V in alkaline. Interestingly, sustainable energies can power the electrolyzer effectively. The work provides methods for potentially promising and cost-effective electrocatalysts.

Unique CoP Microflower Decorated with Phosphorous‐Enriched PtP2 onto Nickel Foam with Interfacial Electronic Interactions to Boost Alkaline Water‐Splitting

AbstractThe development of stable and efficient electrocatalysts for overall freshwater/seawater water‐splitting has received significant attention. In this study, the fabrication and electrocatalytic properties of phosphorus‐enriched PtP2 dispersed on CoP (PtP2/CoP) for HER and OER in both alkaline fresh/seawater media are described. Physical characterization and density functional theory calculations reveal that strong electronic interfacial interactions between PtP2 and CoP optimized the reaction kinetics by regulating the adsorption/desorption of intermediates and the cleavage of reactants. Additionally, operando electrochemical impedance spectroscopy reveals that PtP2/CoP significantly decreased phase angle with increasing applied potential compared with CoP, demonstrating that the construction of heterostructure provides a faster charge transfer on the surface and in the inner layer. Notably, the catalyst only requires overpotentials of 101 and 298 mV to achieve a benchmark of 100 mA cm−2 in alkaline freshwater for HER and OER. Moreover, the prepared catalyst featured overpotentials of 108 and 330 mV in an alkaline seawater electrolyte. Furthermore, a stable and high‐efficiency water electrolysis operation can be achieved using PtP2/CoP as both the anode and cathode (1.63 V@100 mA cm−2) coupled with satisfactory durability. This finding provides a deeper comprehension of the interaction of Pt‐less compounds and matrix in electrocatalysis for bifunctional electrocatalysts.

Triphasic Ni2P-Ni12P5-Ru with Amorphous Interface Engineering Promoted by Co Nano-Surface for Efficient Water Splitting.

This research designs a triphasic Ni2P-Ni12P5-Ru heterostructure with amorphous interface engineering strongly coupled by a cobalt nano-surface (Co@NimPn-Ru) to form a hierarchical 3D interconnected architecture. The Co@NimPn-Ru material promotes unique reactivities toward hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline media. The material delivers an overpotential of 30mV for HER at 10mAcm-2 and 320mV for OER at 50 mAcm-2 in freshwater. The electrolyzer cell derived from Co@NimPn-Ru(+,-) requires a small cell voltage of only 1.43V in alkaline freshwater or 1.44V in natural seawater to produce 10mA cm-2 at a working temperature of 80°C, along with high performance retention after 76h. The solar energy-powered electrolyzer system also shows a prospective solar-to-hydrogen conversion efficiency and sufficient durability, confirming its good potential for economic and sustainable hydrogen production. The results are ascribed to the synergistic effects by an exclusive combination of multi-phasic crystalline Ni2P, Ni12P5, and Ru clusters in presence of amorphous phosphate interface attached onto cobalt nano-surface, thereby producing rich exposed active sites with optimized free energy and multi open channels for rapid charge transfer and ion diffusion to promote the reaction kinetics.

Hetero MOF‐On‐MOF of Ni‐BDC/NH2‐MIL‐88B(Fe) Enables Efficient Electrochemical Seawater Oxidation

AbstractSeawater electrolysis is a sustainable technology for producing hydrogen that would neither cause global freshwater shortages nor create carbon emissions. However, this technology is severely hampered by the insufficient stability and the competition from the chlorine evolution reaction (ClER) in actual application. Herein, a metal–organic framework (MOF)‐on‐MOF heterojunction (Ni‐BDC/NH2‐MIL‐88B(Fe)) denoted as (Ni‐BDC/NM88B(Fe)) is synthesized as an effective oxygen evolution reaction (OER) electrocatalyst for high‐performance seawater electrolysis, which exhibits a long stability of 200 h and low overpotentials of 232 and 299 mV at 100 mA cm−2 in alkaline freshwater and seawater solution, respectively. The exceptional performance is attributed to the rapid self‐reconstruction of Ni‐BDC/NM88B(Fe) to produce NiFeOOH protective layer, thereby avoiding ClER‐induced dissolution. Moreover, the interface interaction between Ni‐BDC and NM88B(Fe) could form the Ni─O─Fe bonds in Ni‐BDC/NM88B(Fe) to promote the electron transfer and lower the energy barrier of the rate‐determining step, thereby accelerating the OER. These electrochemical properties make it intriguing candidate as an efficient electrocatalyst for practical alkaline seawater electrolysis.

Borate Anion‐Intercalated NiV‐LDH Nanoflakes/NiCoP Nanowires Heterostructures for Enhanced Oxygen Evolution Selectivity in Seawater Splitting

AbstractResourceful and inexpensive seawater direct splitting omits the desalination process and effectively increases the efficiency of hydrogen energy generation. However, the development of seawater splitting is hampered by the competing selectivity challenges from anodic oxygen evolution reaction (OER) and chlorine evolution reaction and the issues of electrode corrosion. Herein, the borate anion‐intercalated NiV‐LDH nanoflakes/NiCoP nanowires heterostructures supported on Ni foam (2D/1D NiV‐BLDH/NiCoP/NF) is synthesized. Theoretical calculations show that a small amount of V atom doping in Ni(OH)2 is favorable for changing the electronic environment around Ni atoms via bridging Ni─O, which can construct Ni─O─V to accelerate electron transfer and promote catalytic activity. The borate anions (B(OH)4−) intercalation not only results in the good hydrophilicity and high OH− selectivity but also weakens the adsorption of chlorine (Cl−), which effectively restrains the chlorine evolution reaction. Thus, the component optimized NiV0.1‐BLDH/NiCoP/NF electrocatalyst only requires 268 mV overpotential to reach 100 mA cm−2 for OER in an alkaline environment. Particularly, the NiCoP/NF||NiV0.1‐BLDH/NiCoP/NF cell exhibits attractive overall water splitting performance with a low voltage of 1.46 and 1.53 V at 10 mA cm−2 in alkaline freshwater and alkaline seawater, respectively. The design strategy of this electrocatalyst provides a new avenue for seawater splitting.

Nitrogen-doped carbon layer coated Co(OH)F/CoP2 nanosheets for high-current hydrogen evolution reaction in alkaline freshwater and seawater.

Utilizing renewable energy such as offshore wind power to electrolyze seawater for hydrogen production offers a sustainable development pathway to address energy and climate change issues. In this study, by incorporating nitrogen-doped carbon quantum dots (N-CDs) into precursors, we successfully synthesized a nitrogen-doped carbon (NC)-layer-coated Co(OH)F/CoP2 catalyst NC@Co(OH)F/CoP2/NF loaded on nickel foam (NF). The introduction of N-CDs induced significant morphology change of the catalyst, facilitating the exposure of numerous active sites, ensuring the presence of catalytically active species CoP2 in nanoparticle form and avoiding agglomeration, which was advantageous to enhancing the overall hydrogen evolution reaction (HER) activity of the catalyst. The formation of Co-N bonds accelerated electron transfer, regulated the electronic structure, and optimized the catalyst's adsorption capacity for H* intermediates, which resulted in remarkably improved HER performance. In addition, Co(OH)F can also serve as a structural support, preventing the catalyst from collapsing during the HER catalytic process. NC@Co(OH)F/CoP2/NF exhibited excellent HER activity in alkaline freshwater and alkaline seawater, respectively requiring overpotentials of only 107 and 128 mV to achieve a current density of 100 mA cm-2. More importantly, it also demonstrated excellent HER activity at high current densities, with overpotentials of 189 and 237 mV at a current density of 1000 mA cm-2 in alkaline freshwater and alkaline seawater, respectively. This work provides new insights into the design and construction of highly efficient HER catalysts for applications in alkaline freshwater and seawater.

Multiphase interface coupling of Ni-based sulfide composites for high-current-density oxygen evolution electrocatalysis in alkaline freshwater/simulated seawater/seawater.

Constructing highly efficient electrocatalysts is vital to enhance oxygen evolution reaction (OER) performance at industrially relevant current densities. Herein, three-phase coupled Ni3S2/r-NiS/h-NiS composites are grown in situ on Ni foam (NNSN/NF) via a one-step solvothermal approach. The as-prepared composites need overpotentials of only 377 mV, 451 mV and 476 mV at 1000 mA cm-2 for the OER in alkaline freshwater, simulated seawater and seawater, respectively. In addition, the optimized catalyst exhibited long-term durability at 300 mA cm-2. Our work clarifies designing and preparing cost-effective Ni-based sulfide electrocatalysts for the OER in alkaline freshwater/simulated seawater/seawater under industrially relevant current densities.

Iron-impregnated cellulosic carbon as an effective electrocatalyst for seawater oxidation.

The quest for cost effective but active electrocatalysts for water oxidation is at the forefront of research towards hydrogen economy. In this regard, bamboo as biomass derived N-doped cellulosic carbon has shown potential electrocatalytic performance towards water oxidation. The impregnation of optimum metallic Fe boosts the performance further, achieving an overpotential value of 238 mV at a benchmark current density of 10 mA cm-2. Owing to its promising OER performances in alkaline freshwater, the electrocatalyst was further explored in alkaline saline water and alkaline real seawater, exhibiting overpotentials of 272 mV and 280 mV, respectively, to reach 10 mA cm-2 current density. Most importantly, the protective graphitic multilayer surrounding the metallic Fe allowed the electrocatalyst to demonstrate excellent durability over 30 h even at a high current density in alkaline real seawater electrolyte.