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The exploration of new heterojunction materials is of great significance in reducing the cost of existing noble metal catalysts and thus realizing the large-scale application of electrocatalytic hydrolysis technology. Herein, a novel CoP/CoMoP2 heterojunction was synthesized and served as a hydrogen evolution reaction (HER) electrocatalyst. The heterojunction has morphology of nanoporous structure, which is conducive to exposing more active sites and facilitating bubbles transport. The charge distribution is optimized by a strong interface interaction between CoP and CoMoP2. The catalyst's conductivity and the adsorption properties of the intermediates have both been enhanced. CoP/CoMoP2 demonstrates excellent HER activity with an overpotential of 93.6 mV at 10 mA·cm−2, which is competitive with the reported performance of analogous electrocatalysts. This work provides insights into the development of innovative phosphide-based heterojunction electrocatalysts. [ABSTRACT FROM AUTHOR]

The fabrication of heterointerface materials with hierarchical morphologies more than two levels is a challenging yet promising approach to achieve optimal electrocatalyst for hydrogen evolution reaction (HER). Here, using a facile two-step method, we are able to prepare the Ni2P/(Co,Ni)OOH heterointerface with a three-level hierarchy morphology. The multiple levels of hierarchy structures not only offer considerable area for active sites loading, but also facilitate the substance transportation, both beneficial for HER. Meanwhile, the strong charge transfer at the Ni2P/(Co,Ni)OOH heterointerface eliminates the spin asymmetry and achieves the thermos-neutral adsorption of active H species. Moreover, the resulted Coulomb attraction stacks the two materials firmly, facilitating the stability. Density functional theory (DFT) and in-situ Raman measurements reveal the sufficient Ni atoms acting as the active sites. With these merits, the Ni2P/(Co,Ni)OOH exhibits much better HER activity than the separate Ni2P or (Co,Ni)OOH, affording a current density of 100 mA/cm2 at an overpotential of 169 mV and a Tafel slope of 41 mV/dec, when tested in alkaline electrolyte. This work provides inspiration for optimizing the intrinsic HER activity utilizing multiple-level hierarchy structures. [ABSTRACT FROM AUTHOR]

The electrocatalytic hydrogen evolution activity of transition metal sulfide heterojunctions are significantly increased when compared with that of a single component, but the mechanism behind the performance enhancement and the preparation of catalysts with specific morphologies still need to be explored. Here, we prepared a Co9S8/MoS2 heterojunction with microsphere morphology consisting of thin nanosheets using a facile two-step method. There is electron transfer between the Co9S8 and MoS2 of the heterojunction, thus realizing the redistribution of charge. After the formation of the heterojunction, the density of states near the Fermi surface increases, the d-band center of the transition metal moves downward, and the adsorption of both water molecules and hydrogen by the catalyst are optimized. As a result, the overpotential of Co9S8/MoS2 is superior to that of most relevant electrocatalysts reported in the literature. This work provides insight into the synergistic mechanisms of heterojunctions and their morphological regulation. [ABSTRACT FROM AUTHOR]

The construction of heterostructures is a versatile tactic to enhance catalytic activity. However, it is still elusive to realize the modulation of the interlayer spacing in this way to further improve the performance. Here, strong interfacial coupling between CoSe2 and MoSe2 by constructing CoSe2/MoSe2 heterostructures is achieved. The interlayer spacing of MoSe2 is compressed by 0.3 Å. The enhanced charge transfer is validated by X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy. Coupled with the morphology of hollow microtubes, which can facilitate the exposure of active sites, CoSe2/MoSe2 heterostructures reported here exhibit high activity (119 mV at 10 mA cm−2) and excellent stability with small degradation after 50 h operation, surpassing other analogous powdered electrocatalysts. This work sheds light on the importance of tuning the interlayer spacing to improve electrocatalytic activity. [ABSTRACT FROM AUTHOR]

The coordination environment is crucial for the activity of an electrocatalyst, which defines the interaction between the central and adjacent atoms. In traditional 2D MX2 (M = Mo, W, etc., X = S, Se), M is usually coordinated with 6 X atoms in either trigonal prismatic (2H) or octahedral (1T) polyhedrons. With such a coordination configuration, only the edge X sites exhibit activity for hydrogen evolution reaction (HER). Here, a planar‐coordination transition metal chalcogenide, PdSe2 is reported, as an efficient electrocatalyst for the HER in an alkaline electrolyte. By reducing the spatial polyhedron coordination to planar polygon coordination, the M sites in PdSe2 can be efficiently activated to interact with the adsorptive intermediates. As a result, both Pd and Se atoms act as active sites for hydrogen evolution with neutral adsorption ability. With an overpotential of 138 mV at 10 mA cm−2, this work advances the exploration of planar‐coordination HER electrocatalysts. [ABSTRACT FROM AUTHOR]

Significant efforts have been dedicated to boosting the electrocatalytic activity of Co9S8 for the oxygen evolution reaction (OER); however, with limited improvement in its intrinsic activity, which relies on careful band engineering. Fe possesses one less 3d electron and lower electronegativity than Co, suggesting a higher d‐band center when forming polyhedron with S anions. Here, to improve the intrinsic activity by elevating the d‐band center, the six‐coordinated octahedrons in Co9S8 are redesigned utilizing an Fe‐incorporated topochemical deintercalation method. Through substituting partial Co octahedrons by Fe octahedrons with higher d‐band, the overall d‐band center is regulated to achieve optimized adsorption and thus superior OER activity. With a reduction of 95 mV on the overpotential (at 10 mA cm−2), this work sheds lights on the design of OER catalysts through polyhedron engineering using topochemical deintercalation. [ABSTRACT FROM AUTHOR]