Tuning the Electron Localization of Gold Enables the Control of Nitrogen-to-Ammonia Fixation.

The (photo)electrochemical N2 reduction reaction (NRR) provides a favorable avenue for the production of NH3 using renewable energy in mild operating conditions. Understanding and building an efficient catalyst with high NH3 selectivity represents an area of intense interest for the early stages of development for NRR. Herein, we introduce a CoOx layer to tune the local electronic structure of Au nanoparticles with positive valence sites for boosting conversion of N2 to NH3 . The catalysts, possessing high average oxidation states (ca. 40 %), achieve a high NH3 yield rate of 15.1 µg cm-2 h-1 and a good faradic efficiency of 19 % at -0.5 V versus reversible hydrogen electrode. Experimental results and simulations reveal that the ability to tune the oxidation state of Au enables the control of N2 adsorption and the concomitant energy barrier of NRR. Altering the Au oxidation state provides a unique strategy for control of NRR in the production of valuable NH3 .

Crystalline TiO2 protective layer with graded oxygen defects for efficient and stable silicon-based photocathode.

The trade-offs between photoelectrode efficiency and stability significantly hinder the practical application of silicon-based photoelectrochemical devices. Here, we report a facile approach to decouple the trade-offs of silicon-based photocathodes by employing crystalline TiO2 with graded oxygen defects as protection layer. The crystalline protection layer provides high-density structure and enhances stability, and at the same time oxygen defects allow the carrier transport with low resistance as required for high efficiency. The silicon-based photocathode with black TiO2 shows a limiting current density of ~35.3 mA cm-2 and durability of over 100 h at 10 mA cm-2 in 1.0 M NaOH electrolyte, while none of photoelectrochemical behavior is observed in crystalline TiO2 protection layer. These findings have significant suggestions for further development of silicon-based, III-V compounds and other photoelectrodes and offer the possibility for achieving highly efficient and durable photoelectrochemical devices.

Defect-Enhanced Charge Separation and Transfer within Protection Layer/Semiconductor Structure of Photoanodes.

Silicon (Si) requires a protection layer to maintain stable and long-time photoanodic reaction. However, poor charge separation and transfer are key constraint factors in protection layer/Si photoanodes that reduce their water-splitting efficiency. Here, a simultaneous enhancement of charge separation and transfer in Nb-doped NiOx /Ni/black-Si photoanodes induced by plasma treatment is reported. The optimized photoanodes yield the highest charge-separation efficiency (ηsep ) of ≈81% at 1.23 V versus reversible hydrogen electrode, corresponding to the photocurrent density of ≈29.1 mA cm-2 . On the basis of detailed characterizations, the concentration and species of oxygen defects in the NiOx -based layer are adjusted by synergistic effect of Nb doping and plasma treatment, which are the dominating factors for forming suitable band structure and providing a favorable hole-migration channel. This work elucidates the important role of oxygen defects on charge separation and transfer in the protection layer/Si-based photoelectrochemical systems and is encouraging for application of this synergistic strategy to other candidate photoanodes.

Plasma-Assisted Synthesis and Surface Modification of Electrode Materials for Renewable Energy.

Renewable energy technology has been considered as a "MUST" option to lower the use of fossil fuels for industry and daily life. Designing critical and sophisticated materials is of great importance in order to realize high-performance energy technology. Typically, efficient synthesis and soft surface modification of nanomaterials are important for energy technology. Therefore, there are increasing demands on the rational design of efficient electrocatalysts or electrode materials, which are the key for scalable and practical electrochemical energy devices. Nevertheless, the development of versatile and cheap strategies is one of the main challenges to achieve the aforementioned goals. Accordingly, plasma technology has recently appeared as an extremely promising alternative for the synthesis and surface modification of nanomaterials for electrochemical devices. Here, the recent progress on the development of nonthermal plasma technology is highlighted for the synthesis and surface modification of advanced electrode materials for renewable energy technology including electrocatalysts for fuel cells, water splitting, metal-air batteries, and electrode materials for batteries and supercapacitors, etc.