The realization of the efficient hydrogen conversion with large current densities at low overpotentials represents the development trend of this field. Here we report the atomic active sites tailoring through a facile synthetic method to yield well-defined Rhodium nanocrystals in aqueous solution using formic acid as the reducing agent and graphdiyne as the stabilizing support. High-resolution high-angle annular dark-field scanning-transmission electron microscopy images show the high-density atomic steps on the faces of hexahedral Rh nanocrystals. Experimental results reveal the formation of stablesp–C~Rh bonds can stabilize Rh nanocrystals and further improve charge transfer ability in the system. Experimental and density functional theory calculation results solidly demonstrate the exposed high active stepped surfaces and various metal atomic sites affect the electronic structure of the catalyst to reduce the overpotential resulting in the large-current hydrogen production from saline water. This exciting result demonstrates unmatched electrocatalytic performance and highly stable saline water electrolysis.

Overall seawater electrolysis is an important direction for the development of hydrogen energy conversion. The key issues include how to achieve high selectivity, activity, and stability in seawater electrolysis reactions. In this report, the heterostructures of graphdiyne-RhO_x-graphdiyne (GDY/RhO_x/GDY) were constructed by in situ-controlled growth of GDY on RhO_xnanocrystals. A double layer interface ofsp-hybridized carbon-oxide-Rhodium (sp-C∼O-Rh) was formed in this system. The microstructures at the interface are composed of active sites ofsp-C∼O-Rh. The obvious electron-withdrawing surface enhances the catalytic activity with orders of magnitude, while the GDY outer of the metal oxides guarantees the stability. The electron-donating and withdrawingsp-C∼O-Rh structures enhance the catalytic activity, achieving high-performance overall seawater electrolysis with very small cell voltages of 1.42 and 1.52 V at large current densities of 10 and 500 mA cm⁻²at room temperatures and ambient pressures, respectively. The compositional and structural superiority of the GDY-derivedsp-C-metal-oxide active center offers great opportunities to engineer tunable redox properties and catalytic performance for seawater electrolysis and beyond. This is a typical successful example of the rational design of catalytic systems.

The deployment of direct methanol fuel cells requires engineering cost-effective and durable electrocatalysts for the methanol oxidation reaction (MOR). As an alternative to noble metals, Ni-based alloys have shown excellent performance and good stability toward the MOR. Herein, we present a series of Ni_3−xCo_xSn₂ colloidal nanoparticles (NPs) with composition tuned over the entire Ni/Co range (0 ≤ x ≤ 3). We demonstrate electrodes based on these ternary NPs to provide improved catalytic performance toward the MOR in an alkaline medium when compared with binary Ni₃Sn₂ NPs. A preliminary composition optimization resulted in Ni_2.5Co_0.5Sn₂ NP-based electrodes exhibiting extraordinary mass current densities, up to 1050 mA mg⁻¹, at 0.6 V vs. Hg/HgO in 1.0 M KOH containing 1.0 M methanol. This current density was about two-fold higher than that of Ni₃Sn₂ electrodes (563 mA mg⁻¹). The excellent performance obtained with the substitution of small amounts of Ni by Co was concomitant with an increase of the surface coverage of active species and an enhancement of the diffusivity of the reaction limiting species. Additionally, saturation of the catalytic activity at higher methanol concentrations was measured for Ni_3−xCo_xSn₂ NP-based electrodes containing a small amount of Co when compared with binary Ni₃Sn₂ NPs. While the electrode stability was improved with respect to elemental Ni NP-based electrodes, the introduction of small amounts of Co slightly decreased the cycling performance. Additionally, Sn, a key element to improve stability with respect to elemental Ni NPs, was observed to slowly dissolve in the presence of KOH. Density functional theory calculations on metal alloy surfaces showed the incorporation of Co within the Ni₃Sn₂ structure to provide more effective sites for CO and CH₃OH adsorption. However, the relatively lower stability could not be related to CO or CH₃OH poisoning.