Modifying the catalyst's electronic structure is essential for improving the hydrazine oxidation reaction (HzOR) and alkaline hydrogen evolution reaction (HER), but it is still very difficult. We have developed a new heterostructured electrocatalyst in this work using Ru nanosheets and NiCo layered double hydroxides (LDH). In-situ Raman and theoretical studies show that the heterostructure of Ru/NiCo LDH lowers absorption of hydrogen's Gibbs free energy and the d-band center of Ru/NiCo LDH (from −1.7250 to −1.3341 eV), causing the directed development of interfacial H2O (ΔGH*, from 1.65 to 0.23 eV). With an overpotential of 19 and 75 mV to achieve 10 and 100 mA cm−2 for HER, these beneficial characteristics provide the Ru/NiCo LDH with exceptional electrocatalytic capabilities. For HzOR, 10 and 100 mA cm−2 may be produced using just −118 and−112 mV, respectively. The Ru/NiCo LDH electrolyzer also only needs 22 and 223 mV to produce 10 and 100 mA cm−2, respectively. This work lays the groundwork for developing bifunctional catalysts for the green hydrogen industry. © 2025

Although ultrathin noble-metal nanosheets have arisen as promising high-efficient electrocatalysts, their catalytic behaviors are still far to be satisfied due to lacking of additional active sites on the basal plane of 2D structure. Herein, partially amorphization strategy is adopted to construct localized amorphous area in ultrathin RuO2 nanosheets by doping Mn. This strategy endows the MnRuOx catalyst enriched basal plane active sites, channels for mass transfer, amorphous/crystalline interfaces, and thus a superior HER activity. Impressively, the optimal MnRuOx NSs-250, which is achieved by annealing at 250 °C, shows excellent HER performance within alkaline condition with a low overpotential of only 31mV at 10mA cm-2 and a small Tafel slope of 46.7mV dec-1 which is superior to that of commercial Pt/C catalysts. The key role of localized amorphization on the enhanced HER properties of MnRuOx NSs-250 is determined by in situ Raman spectroscopy and theoretical calculations. It is found that Mn doping can promote the adsorption/desorption of H2O, thus inducing the electron redistribution at the amorphous/crystalline interfaces and accelerating the Volmer step in alkaline HER. This work provides a valuable guidance for improving the performance and stability of other electrocatalysts for alkaline HER applications. © 2025 Wiley‐VCH GmbH.

The hydrogen evolution reaction (HER) performance of Pt-based electrocatalyts in full pH range can be improved by employing Fe3O4 support to generate the strong metal-support interaction (MSI) effect, which is still rarely reported. Herein, the rod- shaped Fe3O4 supported Pt nanoparticles composite on carbon cloth (CC) (Pt-Fe3O4/CC) is obtained by hydrothermal method and the followed Atomic Layer Deposition method (ALD). The experimental and theoretical calculation results prove that the charges transfer from Pt to Fe3O4, and the strong MSI between Fe3O4 and Pt nanoparticles is generated. Thus, the intrinsic activity and stability of Pt is greatly improved, optimizing the H adsorption on the catalyst surface and greatly promoting hydrogen (H2) formation. The Pt-Fe3O4/CC catalyst exhibits excellent HER performance under alkaline, neutral and acidic conditions, with overpotentials of 22 mV, 59 mV and 29 mV, respectively, to drive a current density of 10 mA cm−2. And its overpotentials are 79 mV and 288 mV under alkaline and neutral conditions at a current density of 100 mA cm−2, respectively, which are significantly lower than those of Pt/C (112 mV and 389 mV). Meanwhile, the catalyst has excellent stability under alkaline and neutral conditions. This research proposes a novel approach for the strategic design of high-performance HER catalysts. © 2025

The structural stability of supported metal nanoparticles determines the activity and longevity of heterogeneous catalysts. Unfortunately, the chemical/thermal working environment inevitably accelerates metal sintering to larger crystallites that leads to the degradation of catalytic performance. Here, we demonstrate that the distribution of defects in carbon support as an inherent parameter plays a crucial role in catalyst sintering. Based on in-situ transmission electron microscopy studies, the strong metal-support interaction between platinum (Pt) nanoparticles and defect-rich graphene nanoflakes largely suppresses metal sintering up to 700 °C. Particularly, the optimal carbon support can be achieved in the annealing process, in which the mass transfer and charge transport can be enhanced by accurately manipulating the distribution of defects in carbon matrix and graphitization degree. It is worth noting that the screened Pt/GNs-300 exhibits impressive oxygen reduction reaction performance with high half-wave potential (0.91 V), mass activity (108.1 A g–1Pt) and excellent stability. By its ascendancy in ORR, the Pt/GNs-300 exhibits a high open-circuit voltage of 1.41 V and a maximum power density of 198.6 mW cm−2 in Zn-air battery, implying its brilliant practicability. This work paves a pathway for achieving sinter-resistant metal-loaded catalysts in energy electrocatalysis. © 2024 Elsevier Ltd

While dual-atom catalysts benefiting from synergetic interatomic interactions have inspired the development of emerging catalysts, the role of atomic interactions on the catalytic selectivity and activity has yet to be clearly discovered. Herein, two-types of Pt dual-atom active sites, Pt dimers (2Pt) with an interatomic distance of 2.6 angstrom and Pt pairs (Pt2) at a distance of 0.9 angstrom, are fabricated by anchoring onto cationic vacancy-rich nickel-based hydroxide (Pt@NiFeCo-E). It reveals that 2Pt sites are favorable for hydrogen evolution reaction (HER) while Pt2 sites are active towards oxygen evolution reaction (OER). The coexistence of two types of Pt dual atoms endows the bifunctional activity, which reached an overpotential of 14 mV@10 mA cm(-2) for HER, an overpotential of 234 mV@100 mA cm(-2) for OER, and an effective overall water splitting reaction (OWS) in alkaline at an overpotential of 1.42 V to reach 10 mA cm(-2) and at 100 mA cm(-2) for 50 h. This work not only clarifies a new mechanism in manipulating the selectivity of dual-atom catalysts via controlling the interatomic distance, but also paves a pathway for designing novel high-efficient bifunctional catalysts.

Developing highly efficient nonnoble bifunctional electrocatalysts for both the H-2 evolution reaction (HER) and O-2 evolution reaction (OER) is essential but challenging for overall water splitting (OWS). Ni based catalysts are proved as promising candidates for water splitting, which usually undergo surface reconstruction by transforming into nickel oxyhydroxides as active sites. Although evidence suggests that the reconstruction originates from the exchange of surface lattice oxygen with the OH-in the electrolyte under electric field, modulating the reconstruction of Ni based catalysts remains a great challenge. Herein, we propose an edge sites enrichment strategy to promote the active phase evolution. The one-step synthesized ultrathin Ni3S2/NiO nanomeshes exhibited an ultrathin porous structure which contain abundant edge sites and Ni3S2/NiO in-plane interface sites. Owing to the unique structure, Ni3S2/NiO nanomeshes possessed an affinity feature to proton and OH-, resulting in a faster reconstruction from Ni3S2 to Ni(OH)(2) than Ni3S2 bulk which subsequently converted into gamma-NiOOH and a lower adsorption barrier for H*. Consequently, the Ni3S2/NiO nanomeshes exhibited outstanding OER activity (300 mV at 200 mA cm(-2)) and unexpected HER activity (73 mV at 10 mA cm(-2)) in 1.0 M KOH. Remarkably, the nanomeshes achieved an ultralow voltage of 1.41 Vat 10 mA cm(-2) with excellent stability for overall water splitting, which prevailed over most of the reported catalysts. Moreover, the nanomeshes performed a H-2 yield of 900 mu mol/h in a solar-assisted water splitting system with a H-2 minimum sales price of $1.77/kg, much lower than that of the commercial catalyst ($7.18/kg). This work sets a new benchmark of monometallic bifunctional catalysts for industrial water splitting and provides new insights into the synthesis of 2D nanomeshes.

Optimizing the electronic structure of an electrocatalyst has been supposed to a valid approach to facilitate the hydrogen evolution reaction (HER) activity. Herein, a core-shell architecture comprising a Pt nanoparticle (NP) encapsulated into single-atomic Co species anchored on nickel iron double layered hydroxide substrate (PtCo-NiFe LDH) was established. The PtCo-NiFe LDH catalyst displays the remarkable electrocatalytic HER performance (29 mV@10 mA cm-2), better than the NiFe LDH (183 mV@10 mA cm-2) and commercial Pt/C (30 mV@10 mA cm-2). In addition, it also possesses excellent stability for up to 25 h, and the morphology and structure have hardly undergone any significant changes. It is supposed that the efficient electronic relation between Pt NP and atomically-distributed Co site on NiFe LDH could give rise to plentiful active sites and enhanced conductivity, and thus raise excellent catalytic properties. This work would improve the design and construction of efficient electrocatalysts for a sustainable green energy system.Graphical AbstractThe acquired PtCo-NiFe LDH has been successfully prepared and used as HER electrocatalyst

Electrocatalytic water splitting for hydrogen production is an appealing strategy to reduce carbon emissions and generate renewable fuels. This promising process, however, is limited by its sluggish reaction kinetics and high-cost catalysts. The two-dimensional (2D) transition metal dichalcogenides (TMDCs) have presented great potential as electrocatalytic materials due to their tunable bandgaps, abundant defective active sites, and good chemical stability. Consequently, phase engineering, defect engineering and interface engineering have been adopted to manipulate the electronic structure of TMDCs for boosting their exceptional catalytic performance. Particularly, it is essential to clarify the local structure of catalytically active sites of TMDCs and their structural evolution in catalytic reactions using atomic resolution electron microscopy and the booming in situ technologies, which is beneficial for exploring the underlying reaction mechanism. In this review, the growth regulation, characterization, particularly atomic configurations of active sites in TMDCs are summarized. The significant role of electron microscopy in the understanding of the growth mechanism, the controlled synthesis and functional optimization of 2D TMDCs are discussed. This review will shed light on the design and synthesis of novel electrocatalysts with high performance, as well as prompt the application of advanced electron microscopy in the research of materials science.

ZIF-67-derived Co-N-C catalysts exhibit efficient water-splitting performance and thus have attracted intense research interest. However, the serious Co agglomeration and loss of most N atoms due to high-temperature pyrolysis limit the further improvement of their electrocatalytic performance. Herein, we report a ZIF-67-derived 2D porous N-doped carbon nanosheet decorated with a Co nanoflake catalyst (Co@NC/CC-500) for OER and HER by a facile pyrolysis method at a low temperature of 500 degrees C. Benefiting from the ultrahigh N doping (12 atom %) and uniformly dispersed Co nanoflakes on 2D porous carbon nanosheets, which lead to a high content of Co-N active sites, the Co@NC/CC-500 catalyst exhibits outstanding performance toward the HER and OER with overpotentials of 95 and 183 mV at 10 mA cm(-2) in 1 M KOH, respectively. Furthermore, the alkaline water electrolyzer using Co@NC/CC-500 as the cathode and anode catalysts can achieve a current density of 10 mA cm(-2) at a cell voltage of 1.52 V. This special low-temperature production method may be extensively utilized to create precisely defined monometal or bimetal nanoflakes decorated on 2D porous N-doped carbon nanosheets for diverse electrochemical energy applications.

Platinum group metals (PGM) have yet to be the most active catalysts in various sustainable energy reactions. Their high cost, however, has made maximizing the activity and minimizing the dosage become an urgent priority for the practical applications of emerging technologies. Herein, a novel 2DPd nanomesh structure possessing hole inner reconstructed edges (HIER) with exposed high energy facets and overstretched lattice parameters is fabricated through a facile room-temperature reduction method at gram-scale yields. The HIER enhances the catalytic performance of Pd in electrochemical oxygen reduction reaction (ORR), achieving superior mass activity (MA) of 2.672 A mgPd -1, which is 27.8 fold and 23.6 fold higher, respectively, than those of the commercial Pt/C (0.096 A mgPt -1) and Pd/C (0.113 A mgPd -1) at 0.9 VRHE. Most significantly, in H2-air anion exchange membrane fuel cell (AEMFC) and Zn-air battery (ZAB) applications, this unique Pd catalyst delivers a much-outperformed peak power density of 0.86 and 0.22W cm-2, respectively, compared with 0.54 and 0.13W cm-2 of the commercial Pt/C catalyst, indicating a novel pathway in electrocatalyst designs through HIER engineering. © 2024 Wiley‐VCH GmbH.