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Substituting slow oxygen evolution reaction (OER) with thermodynamically favorable urea oxidation reaction (UOR) is considered as one of the feasible strategies for achieving energy-saving hydrogen production. Herein, a uniform layer of NiMoO4 nanorods was grown on nickel foam by a hydrothermal method. Then, a series of Ni-MoOx/NF-X nanorod catalysts comprising Ni/NiO and MoOx (MoO2/MoO3) were prepared through regulating annealing atmosphere and reduction temperature. The optimized Ni-MoOx/NF-3 with a large accessible specific area can act as a bifunctional catalyst for electrocatalytic anodic UOR and cathodic hydrogen evolution reaction (HER). At a current density of 100 mA cm−2, the introduction of urea can significantly reduce the overpotential of Ni-MoOx/NF-3 by 210 mV compared to OER. In addition, Ni-MoOx/NF-3 has a higher intrinsic activity than other catalysts. It only requires −0.21 and 1.38 V to reach 100 mA cm−2 in HER and UOR, respectively. Such an excellent performance can be attributed to the synergistic function between Ni and MoOx. The presence of metallic Ni and reduced MoOx in pairs is beneficial for improving the electrical conductivity and modulating the electronic structure, resulting in enhancing the electrocatalytic performance. When assembling Ni-MoOx/NF-3 into an overall urea–water splitting system, it can achieve energy-saving hydrogen production and effective removal of urea-rich wastewater. [ABSTRACT FROM AUTHOR]

Using urea oxidation reaction (UOR) instead of oxygen evolution reaction (OER) is one of promising strategies for significantly diminish power consumption for hydrogen production from electrochemical water splitting. The electrocatalysts with cost-effective, multifunctional and high-performance are urgently required for enhancing UOR and hydrogen evolution reaction (HER), but this remains a challenge. Herein, we designed a bifunctional Ni(OH) x /p-Ni catalyst by electrochemical oxidation of Ni(OH) 2 in-situ grown on the surface of porous Ni membrane (p-Ni) to generate more abundant high-valence Ni3+ active species, which is favorable for reducing the energy barrier of electrochemical reaction. At the same time, a large number of metallic oxygen bonds (Ni–O) were formed to optimize the reaction kinetics of the electrochemical process, thus promoting the overall urea electrolysis efficiency. In 1.0 M KOH with 0.3 M urea, the optimized Ni(OH) x /p-Ni only requires potentials of 1.38 V and 0.22 V to obtain a current density of 100 mA cm−2 for UOR and HER, respectively. Notably, by assembling the Ni(OH) x /p-Ni as the cathode and anode for hydrogen production from urea-assisted water splitting, it can drive a current density of 100 mA cm−2 at a low voltage of 1.52 V and has excellent stability. This work provides a feasible strategy for design efficiently non-noble metal electrocatalysts for energy-saving hydrogen production and purifying urea-rich wastewater. [Display omitted] • Nanoflowers Ni(OH) 2 /p-Ni was grown on porous Ni membrane by solvthremal oxidation. • Electrochemical oxidation in-situ generates abundant Ni3+ active species. • The Ni(OH) x /p-Ni exhibited excellent bifunctional performance for HER/UOR. • Replacing OER with UOR can significantly save energy for hydrogen production. [ABSTRACT FROM AUTHOR]

Efficient hydrogen production by water electrolysis is primarily restrained by imperfect over-potential and poor reaction dynamics on oxygen evolution reaction (OER). Thermodynamically favourable urea oxidation reaction (UOR) is a class of promising routes for substituting sluggish OER and for coupling with cathodic hydrogen production because of smaller equilibrium potential (0.37 V) than that of OER (1.23 V). Herein, a versatile Ru-NiO/p-Ni catalyst was prepared through in-situ generating nickel hydroxide nanosheets on the surface of ordered porous Ni, then doping low Ru and annealing treatment. The optimized Ru-NiO/p-Ni displayed outstanding activity and stability towards hydrogen evolution reaction (HER), OER and UOR with potentials of −0.13 V, 1.57 V, and 1.39 V at 100 mA cm−2, respectively. Ru-NiO/p-Ni‖Ru-NiO/p-Ni can achieve 100 mA cm−2 in urea-aided water splitting at a voltage of only 1.58 V, which is prominently 170 mV smaller than the voltage of water electrolysis (1.75 V). The excellent electrocatalytic performance is owing to the outstanding inherent activity generated by cooperative effect of Ru and NiO, along with rich defect and active centre of Ru-NiO/p-Ni supplied by the large surface area of 3D porous structure. The formation of more rich Ni active species with a high valence through transport of electrons between Ru and Ni is favourable to promoting the dissociation of urea molecules, eventually improving UOR. Therefore, it can facilitate urea-aided water splitting, which provides a valuable strategy for constructing versatile catalysts for a cathodic energy-efficient hydrogen production coupled with other anodic oxidation reactions. [Display omitted] • Replacing OER with UOR is apparently energy-saving for hydrogen production. • Ru activates NiO nanosheets grown in-situ on porous Ni to obtain more active sites. • Electron transfers of Ru and Ni species significantly promotes HER/OER/UOR. [ABSTRACT FROM AUTHOR]

Designing highly active and durable catalysts is considered to be crucial for enhancing hydrogen evolution reaction (HER) from water electrolysis. Although some studies indicate that anatase TiO 2 is a promising candidate for electrolytic hydrogen evolution reaction, the influence of different crystalline phases of TiO 2 on the supported Ru catalysts for electrocatalytic HER performance is rarely systematically explored. Herein, a series of Ru/TiO 2 -X (X = R (Rutile), A (Anatase), and P25) catalysts were prepared to investigate the influence of the rutile and anatase phases of TiO 2 on the catalytic activity of Ru catalysts in HER. The findings demonstrate that the HER activity is much affected by the variation of the titania structure, when other factors are kept constant. The 15Ru/TiO 2 -R-H 2 has superior HER performance with a small overpotential of 63 mV to achieve a current density of 10 mA cm−2 in acidic electrolyte and 99 mV in alkaline electrolyte compared to 15Ru/TiO 2 -A-H 2 and 15Ru/TiO 2 -P25-H 2. This might be attributed to the faster electron transfer and lower Fermi level caused by the oxygen vacancy (V O) and strong metal-support interaction (SMSI), along with the exposure of active sites afforded by the highly dispersed ruthenium nanoparticles on the rutile TiO 2. Our results indicate that the presence of rutile TiO 2 support alone is adequate to maintain Ru in its most active form and make it a more performing catalyst, compared to anatase titania and P25. • Ru is supported on different crystalline phase of TiO 2 for electrocatalytic HER. • Partial Ru is incorporated the lattice of TiO 2 -R with SMSI effect. • Highly dispersed Ru and rich V O promote electrocatalytic HER. • Electron transfer from V O and Ti to surface Ru is conducive to optimizing HER. [ABSTRACT FROM AUTHOR]