Research Article Issue
Electronic engineering of Co-Ru diatomic sites and Ru nanoparticles for synergistic promotion of hydrogen evolution
Nano Research 2024, 17 (5): 3714-3723
Published: 20 November 2023

The coexistence of multi-component active sites like single-atom sites, diatomic sites (DAS) and nanoclusters is shown to result in superior performances in the hydrogen evolution reaction (HER). Metal diatomic sites are more complex than single-atom sites but their unique electronic structures can lead to significant enhancement of the HER kinetics. Although the synthesis and identification of DAS is usually challenging, we report a simple access to a diatomic catalyst by anchoring Co-Ru DAS on nitrogen-doped carbon supports along with Ru nanoparticles (NPs). Experimental and theoretical results revealed the atomic-level characteristics of Co-Ru sites, their strong electronic coupling and their synergy with Ru NPs within the catalyst. The unique electronic structure of the catalyst resulted in an excellent HER activity and stability in alkaline media. This work provides a valuable insight into a widely applicable design of diatomic catalysts with multi-component active sites for highly efficient HER electrocatalysis.

Research Article Issue
Accelerating water dissociation at carbon supported nanoscale Ni/NiO heterojunction electrocatalysts for high-efficiency alkaline hydrogen evolution
Nano Research 2023, 16 (4): 4742-4750
Published: 15 December 2022

The synergistic catalysis of heterojunction electrocatalysts for the multi-step process in hydrogen evolution reaction (HER) is a promising approach to enhance the kinetics of alkaline HER. Herein, we proposed a strategy to form nanoscale Ni/NiO heterojunction porous graphitic carbon composites (Ni/NiO-PGC) by reduction-pyrolysis of the preformed Ni-metal-organic framework (MOF) under H2/N2 atmosphere. Benefiting from low electron transfer resistance, increased number of active sites, and unique hierarchical micro-mesoporous structure, the optimized Ni/NiO-PGC10-1-400 exhibited excellent electrocatalytic performance and robust stability for alkaline HER (η10 = 30 mV, 65 h). Density functional theory (DFT) studies revealed that the redistribution of electrons at the Ni/NiO interface enables the NiO phase to easily initiate the dissociation of alkaline H2O, and shifts down the d-band center of Ni and optimizes the H* adsorption–desorption process of Ni, thereby leading to extremely high HER activity. This work contributes to a further understanding of the synergistic promotion of the multi-step HER processes by heterojunction electrocatalysts.

Research Article Issue
One-pot pyrolysis synthesis of highly active Ru/RuOX nanoclusters for water splitting
Nano Research 2022, 15 (2): 1020-1026
Published: 04 July 2021

Using simple methods to obtain efficient catalysts has been a long-standing goal for researchers. In this work, the employment of a one-pot pyrolysis reaction to achieve molecular confinement, has led to the preparation of ruthenium (Ru)-based nanoclusters in a carbon matrix. A unique feature of the synthetic approach employed is that solvent and substrates were calcined together. As solvent evaporates, during calcination, the substrates form a dense solid which has the effect of limiting the aggregation of Ru centers during the carbonization process. The catalyst prepared in this simple manner showed an impressively high activity with respect to the hydrogen/oxygen evolution reaction (HER/OER). The Ru nanoclusters (Ru NCs), as the hydrogen evolution reaction (HER) catalysts, require ultralow overpotentials of 5 mV and 5.1 mV at –10 mA·cm–2 in 1.0 M KOH, and 0.5 M H2SO4, respectively. Furthermore, the catalyst prepared by the one-pot method has higher crystallinity, a higher Ru content and an ultrafine cluster size, which contributes to its exceptional electrochemical performance. Meanwhile, the RuOX nanoclusters (RuOX NCs), obtained by oxidizing the aforementioned Ru NCs, exhibited good oxygen evolution reaction (OER) performance with an overpotential of 266 mV at 10 mA·cm–2. When applied to overall water splitting, Ru/RuOX nanoclusters as the cathode and anode catalysts can reach 10 mA·cm–2 at cell voltages of only 1.49 V in 1 M KOH.

Research Article Issue
Multiple structural defects in ultrathin NiFe-LDH nanosheets synergistically and remarkably boost water oxidation reaction
Nano Research 2022, 15 (1): 310-316
Published: 03 June 2021

Modifying electrocatalysts nanostructures and tuning their electronic properties through defects-oriented synthetic strategies are essential to improve the oxygen evolution reaction (OER) performance of electrocatalysts. Current synthetic strategies about electrocatalysts mainly target the single or double structural defects, while the researches about the synergistic effect of multiple structural defects are rare. In this work, the ultrathin NiFe layered double hydroxide nanosheets with a holey structure, oxygen vacancies and Ni3+ defects on nickel foam (NiFe-LDH-NSs/NF) are prepared by employing a simple and green H2O2-assisted etching method. The synergistic effect of the above three defects leads to the exposure of more active sites and significant improvement of the intrinsic activity. The optimized catalyst exhibits an excellent OER performance with an extraordinarily low overpotential of 170 mV at 10 mA·cm−2 and a small Tafel slope of 39.3 mV·dec−1 in 1 M KOH solution. Density functional theory calculations reveal this OER performance arises from pseudo re-oxidized metal-stable Ni3+ near oxygen vacancies (Ovac), which suppresses 3d-eg of Ni-site and elevates d-band center towards the competitively low electron-transfer barrier. This work provides a new insight to fabricate advanced electrocatalysts for renewable energy conversion technologies.

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