Towards Long‐Term Photostability of Nickel Hydroxide/BiVO4 Photoanodes for Oxygen Evolution Catalysts via In Situ Catalyst Tuning

Increasing long‐term photostability of BiVO₄ photoelectrode is an important issue for solar water splitting. The NiOOH oxygen evolution catalyst (OEC) has fast water oxidation kinetics compared to the FeOOH OEC. However, it generally shows a lower photoresponse and poor stability because of the more substantial interface recombination at the NiOOH/BiVO₄ junction. Herein, we utilize a plasma etching approach to reduce both interface/surface recombination at NiOOH/BiVO₄ and NiOOH/electrolyte junctions. Further, adding Fe²⁺ into the borate buffer electrolyte alleviates the active but unstable character of etched‐NiOOH/BiVO₄, leading to an outstanding oxygen evolution over 200 h. The improved charge transfer and photostability can be attributed to the active defects and a mixture of NiOOH/NiO/Ni in OEC induced by plasma etching. Metallic Ni acts as the ion source for the in situ generation of the NiFe OEC over long‐term durability.     

Chemical‐Reductant‐Free Electrochemical Deuteration Reaction using Deuterium Oxide

We report a method for the electrochemical deuteration of α,β‐unsaturated carbonyl compounds under catalyst‐ and external‐reductant‐free conditions, with deuteration rates as high as 99 % and yields up to 91 % in 2 h. The use of graphite felt for both the cathode and the anode was key to ensuring chemoselectivity and high deuterium incorporation under neutral conditions without the need for an external reductant. This method has a number of advantages over previously reported deuteration reactions that use stoichiometric metallic reductants. Mechanistic experiments showed that O₂ evolution at the anode not only eliminates the need for an external reductant but also regulates the pH of the reaction mixture, keeping it approximately neutral.     

Photo‐excited Oxygen Reduction and Oxygen Evolution Reactions Enable a High‐Performance Zn–Air Battery

The storage of solar energy in battery systems is pivotal for a sustainable society, which faces many challenges. Herein, a Zn–air battery is constructed with two cathodes of poly(1,4‐di(2‐thienyl))benzene (PDTB) and TiO₂ grown on carbon papers to sandwich a Zn anode. The PDTB cathode is illuminated in a discharging process, in which photoelectrons are excited into the conduction band of PDTB to promote oxygen reduction reaction (ORR) and raise the output voltage. In a reverse process, holes in the valence band of the illuminated TiO₂ cathode are driven for the oxygen evolution reaction (OER) by an applied voltage. A record‐high discharge voltage of 1.90 V and an unprecedented low charge voltage of 0.59 V are achieved in the photo‐involved Zn–air battery, regardless of the equilibrium voltage. This work offers an innovative pathway for photo‐energy utilization in rechargeable batteries.     

Tailoring a Zinc Oxide Nanorod Surface by Adding an Earth-Abundant Cocatalyst for Induced Sunlight Water Oxidation

Herein, a detailed investigation of the surface modification of a zinc oxide (ZnO) nanorod electrode with FeOOH nanoparticles dispersed in glycine was conducted to improve the water oxidation reaction assisted by sunlight. The results were systematically analysed in terms of the general parameters (light absorption, charge separation, and surface for catalysis) that govern the photocurrent density response of metal oxide as photoanode in a photoelectrochemical (PEC) cell. ZnO electrodes surface were modified with different concentration of FeOOH nanoparticles using the spin-coating deposition method, and it was found that 6-layer deposition of glycine-FeOOH nanoparticles is the optimum condition. The glycine plays an important role decreasing the agglomeration of FeOOH nanoparticles over the ZnO electrode surface and increasing the overall performance. Comparing bare ZnO electrodes with the ones modified with glycine-FeOOH nanoparticles an enhanced photocurrent density can be observed from 0.27 to 0.57 mA/cm² at 1.23 V_RHE under sunlight irradiation. The impedance spectroscopy data aid us to conclude that the higher photocurrent density is an effect associated with more efficient surface for chemical reaction instead of electronic improvement. Nevertheless, the charge separation efficiency remains low for this system. The present discovery shows that the combination of glycine-FeOOH nanoparticle is suitable and environmentally-friend cocatalyst to enhance the ZnO nanorod electrode activity for the oxygen evolution reaction assisted by sunlight irradiation.     

Regulating Charge Transfer of Lattice Oxygen in Single‐Atom‐Doped Titania for Hydrogen Evolution

Single‐atom catalysts have attracted much attention. Reported herein is that regulating charge transfer of lattice oxygen atoms in serial single‐atom‐doped titania enables tunable hydrogen evolution reaction (HER) activity. First‐principles calculations disclose that the activity of lattice oxygen for the HER can be regularly promoted by substituting its nearest metal atom, and doping‐induced charge transfer plays an essential role. Besides, the realm of the charge transfer of the active site can be enlarged to the second nearest atom by creating oxygen vacancies, resulting in further optimization for the HER. Various single‐atom‐doped titania nanosheets were fabricated to validate the proposed model. Taking advantage of the localized charge transfer to the lattice atom is demonstrated to be feasible for realizing precise regulation of the electronic structures and thus catalytic activity of the nanosheets.     

Strain Influences the Hydrogen Evolution Activity and Absorption Capacity of Palladium

Strain engineering can increase the activity and selectivity of an electrocatalyst. Tensile strain is known to improve the electrocatalytic activity of palladium electrodes for reduction of carbon dioxide or dioxygen, but determining how strain affects the hydrogen evolution reaction (HER) is complicated by the fact that palladium absorbs hydrogen concurrently with HER. We report here a custom electrochemical cell, which applies tensile strain to a flexible working electrode, that enabled us to resolve how tensile strain affects hydrogen absorption and HER activity for a thin film palladium electrocatalyst. When the electrodes were subjected to mechanically‐applied tensile strain, the amount of hydrogen that absorbed into the palladium decreased, and HER electrocatalytic activity increased. This study showcases how strain can be used to modulate the hydrogen absorption capacity and HER activity of palladium.     

Engineering Platinum–Oxygen Dual Catalytic Sites via Charge Transfer towards Highly Efficient Hydrogen Evolution

A dual‐site catalyst allows for a synergetic reaction in the close proximity to enhance catalysis. It is highly desirable to create dual‐site interfaces in single‐atom system to maximize the effect. Herein, we report a cation‐deficient electrostatic anchorage route to fabricate an atomically dispersed platinum–titania catalyst (Pt₁^O1/Ti_1?xO₂), which shows greatly enhanced hydrogen evolution activity, surpassing that of the commercial Pt/C catalyst in mass by a factor of 53.2. Operando techniques and density functional calculations reveal that Pt₁^O1/Ti_1?xO₂ experiences a Pt?O dual‐site catalytic pathway, where the inherent charge transfer within the dual sites encourages the jointly coupling protons and plays the key role during the Volmer–Tafel process. There is almost no decay in the activity of Pt₁^O1/Ti_1?xO₂ over 300 000 cycles, meaning 30 times of enhancement in stability compared to the commercial Pt/C catalysts (10 000 cycles).     

Synthesis of a Hierarchically Porous C/Co3O4 Nanostructure with Boron Doping for Oxygen Evolution Reaction

Fabricating a low‐cost and highly efficient electrocatalyst is of importance for the development of renewable energy devices. In this work, we have synthesized an ultrafine cobalt oxide nanocatalyst (5–10 nm) doped with boron (BC/Co₃O₄) by using a metal–organic framework as a precursor, which exhibits an excellent catalytic activity for oxygen evolution reaction (OER). Owing to the improvement of accessible active sites by boron doping, the synthesized catalyst can reach a current density of 10 mA cm^?2 at 1.54 V with a low overpotential of 310 mV, superior than those of commercial RuO₂ and N‐doped C/Co₃O₄. This work provides a facile way to develop highly efficient catalysts for electrochemical reactions.