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The altering of electronic states of metal oxides offers a promising opportunity to realize high‐efficiency surface catalysis, which play a key role in regulating polysulfides (PS) redox in lithium–sulfur (Li–S) batteries. However, little effort has been devoted to understanding the relationship between the electronic state of metal oxides and a catalyst's properties in Li–S cells. Herein, defect‐rich heterojunction electrocatalysts composed of ultrathin TiO2‐x nanosheets and carbon nanotubes (CNTs) for Li–S batteries are reported. Theoretical simulations indicate that oxygen vacancies and heterojunction can enhance electronic conductivity and chemical adsorption. Spectroscopy and electrochemical techniques further indicate that the rich surface vacancies in TiO2‐x nanosheets result in highly activated trapping sites for LiPS and lower energy barriers for fast Li ion mobility. Meanwhile, the redistribution of electrons at the heterojunction interfaces realizes accelerated surface electron exchange. Coupled with a polyacrylate terpolymer (LA132) binder, the CNT@TiO2‐x–S electrodes exhibit a long cycle life of more than 300 cycles at 1 C and a high area capacity of 5.4 mAh cm−2. This work offers a new perspective on understanding catalyst design in energy storage devices through band engineering.

Ir‐based binary and ternary alloys are effective catalysts for the electrochemical oxygen evolution reaction (OER) in acidic solutions. Nevertheless, decreasing the Ir content to less than 50 at% while maintaining or even enhancing the overall electrocatalytic activity and durability remains a grand challenge. Herein, by dealloying predesigned Al‐based precursor alloys, it is possible to controllably incorporate Ir with another four metal elements into one single nanostructured phase with merely ≈20 at% Ir. The obtained nanoporous quinary alloys, i.e., nanoporous high‐entropy alloys (np‐HEAs) provide infinite possibilities for tuning alloy's electronic properties and maximizing catalytic activities owing to the endless element combinations. Particularly, a record‐high OER activity is found for a quinary AlNiCoIrMo np‐HEA. Forming HEAs also greatly enhances the structural and catalytic durability regardless of the alloy compositions. With the advantages of low Ir loading and high activity, these np‐HEA catalysts are very promising and suitable for activity tailoring/maximization.

Developing highly efficient catalysts for oxygen evolution reactions (OER) is a key step for rechargeable metal− oxygen batteries and water splitting. Usually, binary NiFe or ternary NiCoFe nano-alloys are used as the OER catalysts. Herein, combining the precursor alloy design with chemical etching, a simple dealloying route is developed to controllably incorporate five or more nonprecious metals into one nanostructured alloy with a naturally oxidized surface, that is, nanoporous high entropy alloys (np-HEAs) covered with high-entropy (oxy)hydroxides (HEOs). It is found that the alloy composition plays a dominant role in the OER activity enhancement with the np-AlNiCoFeX (X = Mo, Nb, Cr) combination showing the highest activity. Forming quinary HEAs also greatly enhances the electrochemical cycling stabilities compared with the ternary and quaternary counterparts. The result indicates the significance of synergistically incorporating five or more metal elements in one single-phase nanostructure, which provides more structural and chemical degrees of freedom to boost the catalytic performance, overcoming the restriction of normal binary or ternary alloys. Multinary transition metal-based np-HEA is a new class of promising catalyst for various important reactions.

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