Rational Design of Heterostructured Nanomaterials for Accelerating Electrocatalytic Hydrogen Evolution Reaction Kinetics in Alkaline Media

Document Type


Corresponding Author(s)

Hong-Fei Cheng(cheng_hongfei@tongji.edu.cn);
Ji-Wei Ma(jiwei.ma@tongji.edu.cn)


Owing to the merits of high energy density, as well as clean and sustainable properties, hydrogen has been deemed to be a prominent alternative energy to traditional fossil fuels. Electrocatalytic hydrogen evolution reaction (HER) has been deemed to be most promising for achieving green hydrogen production, and has been widely studied in acidic and alkaline solutions. In particular, HER in alkaline media has high potential to achieve large-scale hydrogen production because of the increased durability of electrode materials. However, for the currently most prominent catalyst Pt, its HER kinetics in alkaline solution is generally 2-3 orders lower than that occurring in acidic solution because of the low H+ concentration in alkaline electrolyte. Fortunately, construction of heterostructured electrocatalysts has proved to be an efficient strategy for boosting alkaline HER kinetics because of their various structural merits. The synergistic effect is a unique characteristic of heterostructures, which means one functional active site serves as promoter for water dissociation and another one takes charge of moderate hydrogen adsorption, thus synergistically improving HER performance. In addition, each building block of the heterostructures is tunable, providing more flexibility and chances to construct optimal catalysts. Furthermore, due to the presence of Fermi energy difference between the two components at the interface, the electronic structure of each component could be possibly rationally modulated, thus much enhanced HER performance in alkaline electrolyte can be achieved. With a deeper understanding of on nanoscience and rapid development of nanotechnology, more sophisticated alternative designing strategies have been explored for constructing high-performance heterostructured electrocatalysts. This review presents an outline of the latest development of heterostructured catalysts toward alkaline HER and the rational design principles for constructing interfacial heterostructures to accelerate alkaline HER kinetics. The basic reaction pathways of HER in alkaline media are first described, and then emerging efficient strategies to promote alkaline HER kinetics, including synergistic effect, strain effect, electronic interaction, phase engineering, and architecture engineering. Finally, current existing challenges and research opportunities that deserve further investigation are proposed for the consideration of novel heterostructures towards practical applications.

Graphical Abstract


interfacial heterostructures; hydrogen production; water dissociation; hydrogen adsorption; synergistic effect

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