Engineering Electronic Structure of Nitrogen-Carbon Sites by sp3 -Hybridized Carbon and Incorporating Chlorine to Boost Oxygen Reduction Activity.

Development of efficient and easy-to-prepare low-cost oxygen reaction electrocatalysts is essential for widespread application of rechargeable Zn-air batteries (ZABs). Herein, we mixed NaCl and ZIF-8 by simple physical milling and pyrolysis to obtain a metal-free porous electrocatalyst doped with Cl (mf-pClNC). The mf-pClNC electrocatalyst exhibits a good oxygen reduction reaction (ORR) activity (E1/2 =0.91 V vs. RHE) and high stability in alkaline electrolyte, exceeding most of the reported transition metal carbon-based electrocatalysts and being comparable to commercial Pt/C electrocatalysts. Likewise, the mf-pClNC electrocatalyst also shows state-of-the-art ORR activity and stability in acidic electrolyte. From experimental and theoretical calculations, the better ORR activity is most likely originated from the fact that the introduced Cl promotes the increase of sp3 -hybridized carbon, while the sp3 -hybridized carbon and Cl together modify the electronic structure of the N-adjacent carbons, as the active sites, while NaCl molten-salt etching provides abundant paths for the transport of electrons/protons. Furthermore, the liquid rechargeable ZAB using the mf-pClNC electrocatalyst as the cathode shows a fulfilling performance with a peak power density of 276.88 mW cm-2 . Flexible quasi-solid-state rechargeable ZAB constructed with the mf-pClNC electrocatalyst as the cathode exhibits an exciting performance both at low, high and room temperatures.

Design and Synthesis of Noble Metal-Based Alloy Electrocatalysts and Their Application in Hydrogen Evolution Reaction.

Hydrogen energy is regarded as the ultimate energy source for future human society, and the preparation of hydrogen from water electrolysis is recognized as the most ideal way. One of the key factors to achieve large-scale hydrogen production by water splitting is the availability of highly active and stable electrocatalysts. Although non-precious metal electrocatalysts have made great strides in recent years, the best hydrogen evolution reaction (HER) electrocatalysts are still based on noble metals. Therefore, it is particularly important to improve the overall activity of the electrocatalysts while reducing the noble metals load. Alloying strategies can shoulder the burden of optimizing electrocatalysts cost and improving electrocatalysts performance. With this in mind, recent work on the application of noble metal-based alloy electrocatalysts in the field of hydrogen production from water electrolysis is summarized. In this review, first, the mechanism of HER is described; then, the current development of synthesis methods for alloy electrocatalysts is presented; finally, an example analysis of practical application studies on alloy electrocatalysts in hydrogen production is presented. In addition, at the end of this review, the prospects, opportunities, and challenges facing noble metal-based alloy electrocatalysts are tried to discuss.