Design and multilevel regulation of transition metal phosphides for efficient and industrial water electrolysis.

Renewable energy electrolysis of water to produce hydrogen is an effective measure to break the energy dilemma. However, achieving activity and stability at a high current density is still a key problem in water electrolyzers. Transition metal phosphides (TMPs), with high activity and relative inexpensiveness, have become excellent candidates for the production of highly pure green hydrogen for industrial applications. In this mini-review, multilevel regulation strategies including nanoscale control, surface composition and interface structure design of high-performance TMPs for hydrogen evolution are systematically summarized. On this basis, in order to achieve large-scale hydrogen production in industry, the hydrogen evolution performance and stability of TMPs at a high current density are also discussed. Peculiarly, the practical application and requirements in proton exchange membrane (PEM) or anion exchange membrane (AEM) electrolyzers can guide the advanced design of regulatory strategies of TMPs for green hydrogen production from renewable energy. Finally, the challenges and prospects in the future development trend of TMPs for efficient and industrial water electrolysis are given.

Bimetallic metal-organic framework-derived bamboo-like N-doped carbon nanotube-encapsulated Ni-doped MoC nanoparticles for water oxidation.

Molybdenum carbide materials with unique electronic structures have received special attention as water-splitting catalysts, but their structural stability in the alkaline water electrolysis process is not satisfactory. This study reports an in situ pyrolysis method for preparing NiMo-based metal-organic framework (MOF)-derived chain-mail oxygen evolution reaction (OER) electrocatalysts and bamboo-like N-doped carbon nanotube (NCNT)-encapsulated Ni-doped MoC nanoparticles (NiMoC-NCNTs). The NCNTs can provide chain mail shells to protect the inner highly reactive Ni-doped MoC cores from electrochemical corrosion by the alkaline electrolyte and regulate their catalytic properties through charge redistribution. Benefiting from high N-doping with abundant pyridinic moieties and abundant active sites of the periodic bamboo-like nodes, the as-prepared NiMoC-NCNTs display an outstanding activity for the OER with an overpotential of 310 mV at 10 mA cm-2 and a superior long-term stability of 50 h. Density functional theory calculations reveal that the excellent electrocatalytic activity of NiMoC-NCNTs comes from the electron transfer from NiMoC nanoparticles to NCNTs, resulting in a decrease in the local work function at the carbon surface and optimized free efficiencies of OER intermediates on C sites. This work provides an effective approach to improve the structural stability of fragile catalysts by equipping them with carbon-based chain.

The Promising Seesaw Relationship Between Activity and Stability of Ru-Based Electrocatalysts for Acid Oxygen Evolution and Proton Exchange Membrane Water Electrolysis.

The development of electrocatalysts that are not reliant on iridium for efficient acid-oxygen evolution is a critical step towards the proton exchange membrane water electrolysis (PEMWE) and green hydrogen industry. Ruthenium-based electrocatalysts have garnered widespread attention due to their remarkable catalytic activity and lower commercial price. However, the challenge lies in balancing the seesaw relationship between activity and stability of these electrocatalysts during the acid-oxygen evolution reaction (OER). This review delves into the progress made in Ru-based electrocatalysts with regards to acid OER and PEMWE applications. It highlights the significance of customizing the acidic OER mechanism of Ru-based electrocatalysts through the coordination of adsorption evolution mechanism (AEM) and lattice oxygen oxidation mechanism (LOM) to attain the ideal activity and stability relationship. The promising tradeoffs between the activity and stability of different Ru-based electrocatalysts, including Ru metals and alloys, Ru single-atomic materials, Ru oxides, and derived complexes, and Ru-based heterojunctions, as well as their applicability to PEMWE systems, are discussed in detail. Furthermore, this paper offers insights on in situ control of Ru active sites, dynamic catalytic mechanism, and commercial application of PEMWE. Based on three-way relationship between cost, activity, and stability, the perspectives and development are provided.

Optimized Electronic Modification of S-Doped CuO Induced by Oxidative Reconstruction for Coupling Glycerol Electrooxidation with Hydrogen Evolution.

Glycerol (electrochemical) oxidation reaction (GOR) producing organic small molecule acid and coupling with hydrogen evolution reaction is a critical aspect of ensuring balanced glycerol capacity and promoting hydrogen generation on a large scale. However, the development of highly efficient and selective non-noble metal-based GOR electrocatalysts is still a key problem. Here, an S-doped CuO nanorod array catalyst (S-CuO/CF) constructed by sulfur leaching and oxidative remodeling is used to drive GOR at low potentials: It requires potentials of only 1.23 and 1.33 V versus RHE to provide currents of 100 and 500 mA cm-2, respectively. Moreover, it shows satisfactory comprehensive performance (at 100 mA cm-2, Vcell = 1.37 V) when assembled as the anode in asymmetric coupled electrolytic cell. Furthermore, we propose a detailed cycle reaction pathway (in alkaline environment) of S-doped CuO surface promoting GOR to produce formic acid and glycolic acid. Among them, the C-C bond breaking and lattice oxygen deintercalation steps frequently involved in the reaction pathway are the key factors to determine the catalytic performance and product selectivity. This research provides valuable guidance for the development of transition metal-based electrocatalysts for GOR and valuable insights into the glycerol oxidation cycle reaction pathway.

Oriented and robust anchoring of Fe via anodic interfacial coordination assembly on ultrathin Co hydroxides for efficient water oxidation.

The oriented distribution and strong bonding of Fe active sites in multiple metal hydroxides are crucial to modulate activity and stability for efficient oxygen evolution reaction (OER). However, the dispersion and inevitable dissolution of Fe species still need to be addressed through deliberate design. Here, trace amounts of Fe chelated with tannic acid (TA) are precisely anchored to ultrathin Co hydroxides (TF@Co(OH)2-t) through a new anodic interfacial coordination assembly strategy: firstly, the ZIF-67@Co(OH)2 precursor with ultrathin Co(OH)2 nanosheets vertically grown on the shell, provides abundant active sites and sufficient anchoring regions for subsequent TA-Fe coating; secondly, the TA-Fe ligand network quickly and robustly coats the surface of the Co(OH)2via positive potential-driven chronopotentiometry, yielding TF@Co(OH)2-t with good dispersion and controllable Fe species. The TA-Fe network efficiently activates Co species and prevents the dissolution of Fe ions. Physical characterization and DFT simulations reveal that the optimized OER activity with 317 mV at 10 mA cm-2 for TF@Co(OH)2-500 can be attributed to the accelerated electron transfer, increased active sites, and the moderate fall in d-band center levels due to Fe integration. Moreover, prolonged stability is realized benefiting from the robust TA-Fe coating protecting the actives sites.

Ultrahigh activity of molybdenum/vanadium-doped Ni-Co phosphides nanoneedles based on ion-exchange for hydrogen evolution at large current density.

Heteroatom doping is a promising strategy to optimize the electronic structure of transition metal phosphides so enhancing the hydrogen evolution reaction (HER). However, complex and harsh experimental design is often required to achieve homogeneous doping of corresponding elements while achieving the best regulating effect. Herein, a facile ion-exchange (IE) strategy is applied to dope Mo/V species evenly into Ni-Co phosphides under mild conditions while maintaining the nanoneedle morphology. The electrochemical characterization verifies Mo dopants have a better electronic regulation effect on NiCoP crystal than V dopants, corresponding to the better hydrogen evolution performance of Mo-NiCoP/NF. Notably, due to the highly dispersed nanoneedle morphology, the synergistic effect of Ni-Co phosphides, and the optimized electronic structure, Mo-NiCoP/NF demonstrates a higher activity than that of the noble metal Pt/C at the high current density (>99 mA cm-2). The present work is supposed to open new sights for the development of high-performance catalysts by ion-exchange strategy.