Search

The active-site density, intrinsic activity, and durability of Ni-based catalysts are critical to their application in industrial alkaline water electrolysis. This work develops a kind of promoters, the bixbyite-type lanthanide metal sesquioxides (Ln2O3), which can be implanted into metallic Ni by selective high-temperature reduction to achieve highly efficient Ni/Ln2O3 hybrid electrocatalysts toward hydrogen evolution reaction. The screened Ni/Yb2O3 catalyst shows the low overpotential (20.0 mV at 10 mA cm−2), low Tafel slope (44.6 mV dec−1), and excellent long-term durability (360 h at 500 mA cm−2), significantly outperforming the metallic Ni and benchmark Pt/C catalysts. The remarkable hydrogen evolution activity and stability of Ni/Yb2O3 are attributed to that the Yb2O3 promoter with high oxophilicity and thermodynamic stability can greatly enlarge the active-site density, reduce the energy barrier of water dissociation, optimize the free energy of hydrogen adsorption, and avoid the oxidation corrosion of Ni. While renewable H2 evolution will require inexpensive, abundant catalysts, non-noble metals typically show relatively low activities. Here, authors examine lanthanide metal sesquioxide doped metallic Ni and show efficient, stable performances for alkaline H2 evolution electrocatalysis. [ABSTRACT FROM AUTHOR]

Robust and durable non‐precious metal electrocatalysts for the hydrogen evolution reaction (HER) are crucial to realize sustainable hydrogen production by electrocatalytic water splitting. In this work, a superhydrophilic NiCo nanoparticle array coupled with CeO2 is integrated on graphite plate (NiCo–CeO2/GP) by electrodeposition and subsequent high‐temperature selective reduction. The coupled CeO2 can accelerate dissociation of H2O and favor adsorption of hydrogen, prominently boosting the electrocatalytic HER activity of NiCo alloy. Also, the superhydrophilic self‐supported electrode can promote electron conduction, facilitate bubble release, and prevent catalyst shedding, ensuring an efficient and stable working condition. As a result, NiCo–CeO2/GP exhibits an outstanding HER catalytic activity with low overpotentials of 34 mV at 10 mA cm−2 and 140 mV at 500 mA cm−2, as well as remarkable durability in alkaline media. Notably, this catalyst activation strategy by CeO2 is also applicable to other Ni‐based alloys such as NiFe and NiCu, demonstrating its versatility. An alkaline electrolyzer with NiCo–CeO2/GP as cathode and the NiCo(OH)x–CeO2/GP precursor electrode as anode delivers a current density of 10 mA cm−2 at an ultralow potential (1.45 V@10 mA cm−2), surpassing that of the traditional Pt/C||RuO2 electrolyzer (1.54 V@10 mA cm−2). [ABSTRACT FROM AUTHOR]

Developing highly active nonprecious electrocatalysts with superior durability for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial to improve the efficiency of overall water splitting but remains challenging. Here, a novel superhydrophilic Co4N‐CeO2 hybrid nanosheet array is synthesized on a graphite plate (Co4N‐CeO2/GP) by an anion intercalation enhanced electrodeposition method, followed by high‐temperature nitridation. Doping CeO2 into Co4N can favor dissociation of H2O and adsorption of hydrogen, reduce the energy barrier of intermediate reactions of OER, and improve the compositional stability, thereby dramatically boosting the HER performance while simultaneously inducing enhanced OER activity. Furthermore, the superhydrophilic self‐supported electrode with Co4N‐CeO2 in situ grown on the conductive substrate expedites electron conduction between substrate and catalyst, promotes the bubble release from electrode timely and impedes catalyst shedding, ensuring a high efficiency and stable working state. Consequently, the Co4N‐CeO2/GP electrode shows exceptionally low overpotentials of 24 and 239 mV at 10 mA cm−2 for HER and OER, respectively. An alkaline electrolyzer by using Co4N‐CeO2/GP as both the cathode and anode requires a cell voltage of 1.507 V to drive 10 mA cm−2, outperforming the Pt/C||RuO2 electrolyzer (1.540 V@10 mA cm−2). More significantly, the electrolyzer has extraordinary long‐term durability at a large current density of 500 mA cm−2 for 50 h, revealing its potential in large‐scale applications. [ABSTRACT FROM AUTHOR]