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Electrolysis of water to generate hydrogen fuel is an attractive renewable energy storage technology. However, grid-scale fresh-water electrolysis would put a heavy strain on vital water resources. Developing cheap electrocatalysts and electrodes that can sustain seawater splitting without chloride corrosion could address the water scarcity issue. Here we present a multilayer anode consisting of a nickel–iron hydroxide (NiFe) electrocatalyst layer uniformly coated on a nickel sulfide (NiSx) layer formed on porous Ni foam (NiFe/NiSx-Ni), affording superior catalytic activity and corrosion resistance in solar-driven alkaline seawater electrolysis operating at industrially required current densities (0.4 to 1 A/cm²) over 1,000 h. A continuous, highly oxygen evolution reactionactive NiFe electrocatalyst layer drawing anodic currents toward water oxidation and an in situ-generated polyatomic sulfate and carbonate-rich passivating layers formed in the anode are responsible for chloride repelling and superior corrosion resistance of the salty-water-splitting anode.

Rational design of single atom catalyst is critical for efficient sustainable energy conversion. However, the atomic-level control of active sites is essential for electrocatalytic materials in alkaline electrolyte. Moreover, well-defined surface structures lead to in-depth understanding of catalytic mechanisms. Herein, we report a single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets (Ru 1 /D-NiFe LDH). Under precise regulation of local coordination environments of catalytically active sites and the existence of the defects, Ru 1 /D-NiFe LDH delivers an ultralow overpotential of 18 mV at 10 mA cm −2 for hydrogen evolution reaction, surpassing the commercial Pt/C catalyst. Density functional theory calculations reveal that Ru 1 /D-NiFe LDH optimizes the adsorption energies of intermediates for hydrogen evolution reaction and promotes the O–O coupling at a Ru–O active site for oxygen evolution reaction. The Ru 1 /D-NiFe LDH as an ideal model reveals superior water splitting performance with potential for the development of promising water-alkali electrocatalysts. Rational design of single atom catalyst is critical for efficient sustainable energy conversion. Single-atomic-site ruthenium stabilized on defective nickel-iron layered double hydroxide nanosheets achieve superior HER and OER performance in alkaline media.

For nickel-based catalysts, in-situ formed nickel oxyhydroxide has been generally believed as the origin for anodic biomass electro-oxidations. However, rationally understanding the catalytic mechanism still remains challenging. In this work, we demonstrate that NiMn hydroxide as the anodic catalyst can enable methanol-to-formate electro-oxidation reaction (MOR) with a low cell-potential of 1.33/1.41 V at 10/100 mA cm −2 , a Faradaic efficiency of nearly 100% and good durability in alkaline media, remarkably outperforming NiFe hydroxide. Based on a combined experimental and computational study, we propose a cyclic pathway that consists of reversible redox transitions of Ni II -(OH) 2 /Ni III -OOH and a concomitant MOR. More importantly, it is proved that the Ni III -OOH provides combined active sites including Ni III and nearby electrophilic oxygen species, which work in a cooperative manner to promote either spontaneous or non-spontaneous MOR process. Such a bifunctional mechanism can well account for not only the highly selective formate formation but also the transient presence of Ni III -OOH. The different catalytic activities of NiMn and NiFe hydroxides can be attributed to their different oxidation behaviors. Thus, our work provides a clear and rational understanding of the overall MOR mechanism on nickel-based hydroxides, which is beneficial for advanced catalyst design. Understanding the active sites is essential for advanced catalyst design. Here, the authors report a bifunctional mechanism for the methanol electrooxidation reaction using NiMn hydroxide with Ni III and oxygen active sites which work in a cooperative manner to promote either spontaneous or non-spontaneous methanol oxidation.

Single-atom catalysts with maximum metal utilization efficiency show great potential for sustainable catalytic applications and fundamental mechanistic studies. We here provide a convenient molecular tailoring strategy based on graphitic carbon nitride as support for the rational design of single-site and dual-site single-atom catalysts. Catalysts with single Fe sites exhibit impressive oxygen reduction reaction activity with a half-wave potential of 0.89 V vs. RHE. We find that the single Ni sites are favorable to promote the key structural reconstruction into bridging Ni-O-Fe bonds in dual-site NiFe SAC. Meanwhile, the newly formed Ni-O-Fe bonds create spin channels for electron transfer, resulting in a significant improvement of the oxygen evolution reaction activity with an overpotential of 270 mV at 10 mA cm −2 . We further reveal that the water oxidation reaction follows a dual-site pathway through the deprotonation of *OH at both Ni and Fe sites, leading to the formation of bridging O 2 atop the Ni-O-Fe sites. The development of high performance dual-site single-atom catalysts is a promising research direction. Here, the authors report structural dynamics of dual-site nickel-iron single-atom oxygen electrocatalysts under reaction conditions, and proposes a dual-site pathway for the water oxidation reaction.

Glucose electrolysis offers a prospect of value-added glucaric acid synthesis and energy-saving hydrogen production from the biomass-based platform molecules. Here we report that nanostructured NiFe oxide (NiFeO x ) and nitride (NiFeN x ) catalysts, synthesized from NiFe layered double hydroxide nanosheet arrays on three-dimensional Ni foams, demonstrate a high activity and selectivity towards anodic glucose oxidation. The electrolytic cell assembled with these two catalysts can deliver 100 mA cm −2 at 1.39 V. A faradaic efficiency of 87% and glucaric acid yield of 83% are obtained from the glucose electrolysis, which takes place via a guluronic acid pathway evidenced by in-situ infrared spectroscopy. A rigorous process model combined with a techno-economic analysis shows that the electrochemical reduction of glucose produces glucaric acid at a 54% lower cost than the current chemical approach. This work suggests that glucose electrolysis is an energy-saving and cost-effective approach for H 2 production and biomass valorization. Renewable biomass conversion may afford high-value products from common materials, but catalysts usually require expensive metals and exhibit poor selectivities. Here, authors employ nickel-iron oxide and nitride electrocatalysts to produce H 2 and to convert glucose to glucaric acid selectively.

Investigations of the synthesis of multicomponent coatings and their subsequent application to metal substrates to increase the wear resistance of materials is relevant for industry. Nickel compounds obtained from oxidized magnesia-iron nickel ores with a desorption rate of more than 94% were used to create Ni-MoO[sub.3]-WO[sub.3] electroplating. Such composite samples formed from an aqueous alcohol solution reduced the content of sodium and ammonium chlorides. The annealing and dehydration of samples at a temperature of 725 °C in an air atmosphere made it possible to achieve the highest level of crystallinity. In this case, an isomorphic substitution of W atoms by Mo occurs, which is confirmed by electron paramagnetic resonance (EPR) spectroscopy studies. The invariance of the shape of the EPR spectrum with a sequential increase in microwave radiation power revealed the stability of the bonds between the particles. The surface morphology of Ni-MoO[sub.3]-WO[sub.3] films deposited on an Al substrate is smooth and has low roughness. In this case, an increased degree of wear resistance has been achieved. Thus, a recipe for the formation of an electroplating with stable bonds between the components and increased wear resistance was obtained.

NiFe-based oxo-hydroxides are highly active for the oxygen evolution reaction but require complex synthesis and are poorly durable when deposited on foreign supports. Herein we demonstrate that easily processable, Earth-abundant and cheap Fe–Ni alloys spontaneously develop a highly active NiFe oxo-hydroxide surface, exsolved upon electrochemical activation. While the manufacturing process and the initial surface state of the alloys do not impact the oxygen evolution reaction performance, the growth/composition of the NiFe oxo-hydroxide surface layer depends on the alloying elements and initial atomic Fe/Ni ratio, hence driving oxygen evolution reaction activity. Whatever the initial Fe/Ni ratio of the Fe–Ni alloy (varying between 0.004 and 7.4), the best oxygen evolution reaction performance (beyond that of commercial IrO 2 ) and durability was obtained for a surface Fe/Ni ratio between 0.2 and 0.4 and includes numerous active sites (high Ni III /Ni II capacitive response) and high efficiency (high Fe/Ni ratio). This knowledge paves the way to active and durable Fe–Ni alloy oxygen-evolving electrodes for alkaline water electrolysers. NiFe-based oxo-hydroxides are active for the oxygen evolution reaction but suffer from complex synthesis and durability when deposited. Easily processable Fe–Ni alloys with a highly active oxo-hydroxide surface are now shown to pave the way for oxygen-evolving electrodes for alkaline water electrolysers.

Promoting the formation of high-oxidation-state transition metal species in a hydroxide catalyst may improve its catalytic activity in the oxygen evolution reaction, which remains difficult to achieve with current synthetic strategies. Herein, we present a synthesis of single-layer NiFeB hydroxide nanosheets and demonstrate the efficacy of electron-deficient boron in promoting the formation of high-oxidation-state Ni for improved oxygen evolution activity. Raman spectroscopy, X-ray absorption spectroscopy, and electrochemical analyses show that incorporation of B into a NiFe hydroxide causes a cathodic shift of the Ni 2+ (OH) 2  → Ni 3+δ OOH transition potential. Density functional theory calculations suggest an elevated oxidation state for Ni and decreased energy barriers for the reaction with the NiFeB hydroxide catalyst. Consequently, a current density of 100 mA cm –2 was achieved in 1 M KOH at an overpotential of 252 mV, placing it among the best Ni-based catalysts for this reaction. This work opens new opportunities in electronic engineering of metal hydroxides (or oxides) for efficient oxygen evolution in water-splitting applications. While water-splitting electrolysis offers a potential renewable means to store energy, the oxygen evolution half-reaction’s sluggish kinetics limits performances. Here, authors incorporation boron into nickel-iron hydroxide catalysts to promote electrocatalytic water oxidation activities

Electrocatalytic H 2 production from seawater, recognized as a promising technology utilizing offshore renewables, faces challenges from chloride-induced reactions and corrosion. Here, We introduce a catalytic surface where OH – dominates over Cl – in adsorption and activation, which is crucial for O 2 production. Our NiFe-based anode, enhanced by nearby Cr sites, achieves low overpotentials and selective alkaline seawater oxidation. It outperforms the RuO 2 counterpart in terms of lifespan in scaled-up stacks, maintaining stability for over 2500 h in three-electrode tests. Ex situ / in situ analyses reveal that Cr(III) sites enrich OH – , while Cl – is repelled by Cr(VI) sites, both of which are well-dispersed and close to NiFe, enhancing charge transfer and overall electrode performance. Such multiple effects fundamentally boost the activity, selectively, and chemical stability of the NiFe-based electrode. This development marks a significant advance in creating durable, noble-metal-free electrodes for alkaline seawater electrolysis, highlighting the importance of well-distributed catalytic sites. Developing highly active and stable oxygen evolution electrocatalysts is crucial for enabling large-scale hydrogen production from seawater. Here, authors report a robust O 2 -producing electrode for alkaline seawater, highlighting the critical role of distributed sites near the catalytic sites.

While self-healing is considered a promising strategy to achieve long-term stability for oxygen evolution reaction (OER) catalysts, this strategy remains a challenge for OER catalysts working in highly alkaline conditions. The self-healing of the OER-active nickel iron layered double hydroxides (NiFe-LDH) has not been successful due to irreversible leaching of Fe catalytic centers. Here, we investigate the introduction of cobalt (Co) into the NiFe-LDH as a promoter for in situ Fe redeposition. An active borate-intercalated NiCoFe-LDH catalyst is synthesized using electrodeposition and shows no degradation after OER tests at 10 mA cm −2 at pH 14 for 1000 h, demonstrating its self-healing ability under harsh OER conditions. Importantly, the presence of both ferrous ions and borate ions in the electrolyte is found to be crucial to the catalyst’s self-healing. Furthermore, the implementation of this catalyst in photoelectrochemical devices is demonstrated with an integrated silicon photoanode. The self-healing mechanism leads to a self-limiting catalyst thickness, which is ideal for integration with photoelectrodes since redeposition is not accompanied by increased parasitic light absorption. While self-healing catalysts may survive the harsh environments used for oxygen evolution, understanding how to develop such electrocatalysts remains a challenge. Here, authors find cobalt to promote the self-healing of leached iron centers in borate-intercalated nickel-iron-cobalt oxyhydroxides.