Redox Promoted Rapid and Deep Reconstruction of Defect-Rich Nickel Precatalysts for Efficient Water Oxidation.

Understanding the reconstruction mechanism to rationally design cost-effective electrocatalysts for oxygen evolution reaction (OER) is still challenging. Herein, a defect-rich NiMoO4 precatalyst is used to explore its OER activity and reconstruction mechanism. In situ generated oxygen vacancies, distorted lattices, and edge dislocations expedite the deep reconstruction of NiMoO4 to form polycrystalline Ni (oxy)hydroxides for alkaline oxygen evolution. It only needs ≈230 and ≈285 mV to reach 10 and 100 mA cm-2, respectively. The reconstruction boosted by the redox of Ni is confirmed experimentally by sectionalized cyclic voltammetry activations at different specified potential ranges combined with ex situ characterization techniques. Subsequently, the reconstruction route is presented based on the acid-base electronic theory. Accordingly, the dominant contribution of the adsorbate evolution mechanism to reconstruction during oxygen evolution is revealed. This work develops a novel route to synthesize defect-rich materials and provides new tactics to investigate the reconstruction.

Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Phosphorus doping and phosphates coating for nickel molybdate/nickel molybdate hydrate enabling efficient overall water splitting.

Earth-abundant transition metal-based bifunctional electrocatalysts are promising alternatives to noble metals for overall water electrolysis, but restricted by low activity and durability. Herein, a three-dimensional phosphorus-doped nickel molybdate/nickel molybdate hydrate @phosphates core-shell nanorod clusters on nickel foam self-supported electrode was fabricated by a combined hydrothermal and phosphating process. The phosphorus doping and phosphate coating induced by phosphating process bring in a synergistic effect to improve the electrical conductivity, provide abundant active surface sites and accelerate the surface reaction for nickel molybdate/nickel molybdate hydrate (NiMoO4/NiMoO4·nH2O) heterostructures. These advantages enable the self-supported electrode to exhibit high hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity in 1.0 M KOH with low overpotentials of 148 and 260 mV at 10 mA cm-2, respectively. When it was employed both as anode and cathode, a cell voltage of 1.62 V is only required to reach the current density of 10 mA cm-2 in alkaline solution. Especially, the self-supported electrode reveals outstanding durability, which could maintain over 25 h at 10 mA cm-2 for HER, OER or overall water splitting. This work provides a novel avenue to enhance the electrocatalytic performance of the catalysts by synergistically modulating the intrinsic electrical conductivity, active surface sites and surface reaction.

Two-dimensional nickel hydroxide/sulfides nanosheet as an efficient cocatalyst for photocatalytic H2 evolution over CdS nanospheres.

The intriguing features of two-dimensional (2D) materials such as better charge carrier separation and abundant surface reaction sites endow them with potential applications as cocatalysts in photocatalysis. In this paper, a ternary 2D nickel hydroxide/sulfides nanosheet composed of Ni(OH)2, Ni3S2 and NixS6 was loaded on CdS nanospheres by a simple chemical deposition route. The composition of nickel hydroxide/sulfides was determined clearly through an overall analysis using X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. Mott-Schottky, electrochemical impedance, steady-state and time-resolved photoluminescence spectroscopy were used to investigate the charge transfer process in CdS and Ni(OH)2/Ni3S2/NixS6-CdS. The results confirm that a synergistic effect of Ni(OH)2/Ni3S2/NixS6 on CdS has occurred under light irradiation, where the Ni(OH)2 and nickel sulfides act as hole storage and surface reaction sites, respectively, to promote the charge transfer on CdS. The improved charge transfer and separation efficiency as well as the increased surface reaction sites in Ni(OH)2/Ni3S2/NixS6-CdS finally result in a dramatically improved photocatalytic performance. The photocatalytic H2 evolution rate of Ni(OH)2/Ni3S2/NixS6-CdS is ca. 46 times higher than that of CdS, and the photocatalytic stability of CdS is also improved substantially under visible light irradiation.

Sonocatalytic degradation of organic dyes and influence of Al(2)O(3), Y(2)O(3) and Fe(2)O(3) on catalytic activity of TiO(2) under ultrasonic irradiation.

In order to improve the sonocatalytic activity of TiO(2), Al(2)O(3)/TiO(2), Y(2)O(3)/TiO(2) and Fe(2)O(3)/TiO(2) composites were prepared using mechanical mixing, liquid boiling, ultrasonic dispersion and heat-treated methods. And then, a series of degradation experiments were carried out under ultrasonic irradiation. Also, the influences of heat-treated temperature and heat-treated time on the sonocatalytic activity of Al(2)O(3)/TiO(2), Y(2)O(3)/TiO(2) and Fe(2)O(3)/TiO(2), and ultrasonic irradiation time and solution acidity on the sonocatalytic degradation of Acid red B were investigated by UV-vis spectra. It was found that the degradation ratio showed significant increase in the order TiO(2) < Fe(2)O(3)/TiO(2) < Y(2)O(3)/TiO(2) < Al(2)O(3)/TiO(2). And the corresponding percentage degradations are about 37, 45, 52 and 81%, respectively. In addition, for exploring the universality, the degradation of other several organic dyes was also reviewed under the same conditions. Because of good degradation efficiency, this method may be an advisable choice for the treatment of non- or low-transparent wastewaters in the future.

The investigation of sonocatalytic activity of Er3+:YAlO3/TiO2-ZnO composite in azo dyes degradation.

In this work, the emphasis was mainly placed on investigating the sonocatalytic activity of TiO(2)-ZnO mixed with Er(3+):YAlO(3), namely, Er(3+):YAlO(3)/TiO(2)-ZnO composite. It is able to utilize the sonoluminescence light to improve the sonocatalytic degradation of organic dyes. The Er(3+):YAlO(3) as up-conversion luminescence agent was synthesized by sol-gel and auto-combustion method, and then Er(3+):YAlO(3)/TiO(2)-ZnO composite as sonocatalyst were prepared by ultrasonic dispersion and liquids boil method. The prepared up-conversion luminescence agent and composites were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). Acid Red B dye was selected to examine the sonocatalytic activity of Er(3+):YAlO(3)/TiO(2)-ZnO composite. The degradation reaction processes were monitored by UV-vis spectrophotometer and ion chromatogram. The influences on the activity of the Er(3+):YAlO(3)/TiO(2)-ZnO such as Ti/Zn molar ratio, heat-treated temperature and heat-treated time were studied. The results showed that the Er(3+):YAlO(3)/TiO(2)-ZnO composite exhibited a significantly high sonocatalytic activity compared with other catalysts in the degradation of Acid Red B. And the sonocatalyst with 1:1 Ti/Zn molar ratio heat-treated at 550°C for 60min showed the highest sonocatalytic activity. At last, the experiment also indicated that it has a good sonocatalytic activity to degrade other organic dyes.

Spectroscopic investigation on assisted sonocatalytic damage of bovine serum albumin (BSA) by metronidazole (MTZ) under ultrasonic irradiation combined with nano-sized ZnO.

The previous work proved that the bovine serum albumin (BSA) could be damaged under the combined action of ultrasonic irradiation and ZnO. In this work, the assisted sonocatalytic damage of BSA using metronidazole (MTZ) as a sensitizer was further investigated by means of UV-vis and fluorescence spectra. The results indicated that the adding of MTZ could obviously promote the sonocatalytic damage of BSA under ultrasonic irradiation in the presence of nano-sized ZnO powder. Furthermore, it was found that the damage degree of BSA was aggravated by some influencing factors except ionic kind and strength. In addition, the damage site of BSA was also studied with synchronous fluorescence technology. It was found that the damage site was mainly at tryptophan (Trp) residue.

Sonocatalytic degradation of organic dyes and comparison of catalytic activities of CeO2/TiO2, SnO2/TiO2 and ZrO2/TiO2 composites under ultrasonic irradiation.

The CeO(2)/TiO(2), SnO(2)/TiO(2) and ZrO(2)/TiO(2) composites were prepared by dispersing various nano-sized oxides (CeO(2), SnO(2), ZrO(2) and TiO(2)) with ultrasound and mixing TiO(2) with CeO(2), SnO(2) and ZrO(2), respectively, in boiling water in a molar ratio of 4:1, followed by calcining temperature 500 degrees C for 60 min. Then a series of sonocatalytic degradation experiments were carried out under ultrasonic irradiation in the presence of CeO(2)/TiO(2), SnO(2)/TiO(2) and ZrO(2)/TiO(2) composites and nano-sized TiO(2) powder. Also, the influences of heat-treatment temperature and heat-treatment time on the sonocatalytic activities of CeO(2)/TiO(2), SnO(2)/TiO(2) and ZrO(2)/TiO(2) composites, and of irradiation time and solution acidity on the sonocatalytic degradation of Acid Red B were investigated by UV-vis spectra. It was found that the sonocatalytic degradation of Acid Red B shows significant variation in rate and ratio that decreases in order: CeO(2)/TiO(2)>SnO(2)/TiO(2)>TiO(2)>ZrO(2)/TiO(2)>SnO(2)>CeO(2)>ZrO(2), and the corresponding ratios of Acid Red B in aqueous solution are 91.32%, 67.41%, 65.26%, 41.67%, 28.34%, 26.75% and 23.33%, respectively. And that the degradation ratio is only 16.67% under onefold ultrasonic irradiation. Because of the good degradation efficiency, this method may be an advisable choice for the treatment of non- or low-transparent wastewaters in the future.