In-situ construction of 3D hetero-structured sulfur-doped nanoflower-like FeNi LDH decorated with NiCo Prussian blue analogue cubes as efficient electrocatalysts for boosting oxygen evolution reaction
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Electrochemical water splitting is a promising technology for sustainable conversion, storage, and transport of hydrogen energy. Searching for earth-abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts with high activity and durability to replace noble-metal-based catalysts plays paramount importance in the scalable application of water electrolysis. A freestanding electrode architecture is highly attractive as compared to the conventional coated powdery form because of enhanced kinetics and stability. Herein, recent progress in developing transition-metal-based HER/OER electrocatalytic materials is reviewed with selected examples of chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides, hydroxides, and oxyhydroxides. Focusing on self-supported electrodes, the latest advances in their structural design, controllable synthesis, mechanistic understanding, and strategies for performance enhancement are presented. Remaining challenges and future perspectives for the further development of self-supported electrocatalysts are also discussed.
Exceptionally high OER & HER performances were achieved by rationally designing the electrode structure of non-noble NiFe materials. Water electrolysis represents a promising sustainable hydrogen production technology. However, in practical application which requires extremely large current densities (>500 mA cm −2 ), the oxygen evolution reaction (OER) becomes unstable and kinetically sluggish, which is a major hurdle to large-scale hydrogen production. Herein, we report an exceptionally active and binder-free NiFe nanowire array based OER electrode that allows durable water splitting at current densities up to 1000 mA cm −2 up to 120 hours. Specifically, NiFe oxyhydroxide (shell)–anchored NiFe alloy nanowire (core) arrays are prepared via a magnetic-field-assisted chemical deposition method. The ultrathin (1–5 nm) and amorphous NiFe oxyhydroxide is in situ formed on the NiFe alloy nanowire surface, which is identified as an intrinsically highly active phase for the OER. Additionally, the fine geometry of the hierarchical electrode can substantially improve charge and mass (reactants and oxygen bubbles) transfer. In an alkaline electrolyte, this OER electrode can yield current densities of 500 and 1000 mA cm −2 stably over 120 hours at overpotentials of only 248 mV and 258 mV respectively, which are dramatically lower than any recently reported overpotentials. Notably, the integrated alkaline electrolyzer (with pure Ni nanowires as HER electrode) is demonstrated to reach the current density of 1000 mA cm −2 with super low voltage of 1.76 V, outperforming the state-of-the-art industrial catalysts. Our result may represent a critical step towards an industrial electrolyzer for large-scale hydrogen production by water splitting.
A robust oxygen-evolving electrocatalyst for high-performance seawater splitting was developed using a cost-effective and industrially compatible method. Developing energy- and time-saving methods to synthesize active and stable oxygen evolving catalysts is of great significance to hydrogen production from water electrolysis, which however remains a grand challenge. Here we report a one-step approach to grow highly porous S-doped Ni/Fe (oxy)hydroxide catalysts on Ni foam in several minutes under room temperature. This ultrafast method effectively engineers the surface of Ni foam into a rough S-doped Ni/Fe (oxy)hydroxide layer, which has multiple levels of porosity and good hydrophilic features and exhibits extraordinary oxygen evolution reaction (OER) performance in both alkaline salty water and seawater electrolytes. Specifically, the S-doped Ni/Fe (oxy)hydroxide catalyst requires low overpotentials of 300 and 398 mV to deliver current densities of 100 and 500 mA cm −2 , respectively, when directly used as an OER catalyst in alkaline natural seawater electrolyte. Using this OER catalyst together with an efficient hydrogen evolution reaction catalyst, we have achieved the commercially demanded current densities of 500 and 1000 mA cm −2 at low voltages of 1.837 and 1.951 V, respectively, for overall alkaline seawater electrolysis at room temperature with very good durability. This work affords a cost-efficient surface engineering method to steer commercial Ni foam into robust OER catalysts for seawater electrolysis, which has important implications for both the hydrogen economy and environmental remediation.
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