Vapor-assisted engineering heterostructure of 1D Mo3N2 nanorod decorated with nitrogen-doped carbon for rapid pH-Universal hydrogen evolution reaction

Reasonable construction of heterostructure is of significance yet a great challenge towards efficient pH-universal catalysts for hydrogen evolution reaction (HER). Herein, a facial strategy coupling gas-phase nitridation with simultaneous heterogenization has been developed to synthesize heterostructure of one-dimensional (1D) Mo₃N₂ nanorod decorated with ultrathin nitrogen-doped carbon layer (Mo₃N₂@NC NR). Thereinto, the collaborative interface of Mo₃N₂ and NC is conducive to accomplish rapid electron transfer for reaction kinetics and weaken the Mo–H_ads bond for boosting the intrinsic activity of catalysts. As expected, Mo₃N₂@NC NR delivers an excellent catalytic activity for HER with low overpotentials of 85, 129, and 162 mV to achieve a current density of 10 mA cm^?2 in alkaline, acidic, and neutral electrolytes, respectively, and favorable long-term stability over a broad pH range. As for practical application in electrocatalytic water splitting (EWS) under alkaline, Mo₃N₂@NC NR || NiFe-LDH-based EWS also exhibits a low cell voltage of 1.55 V and favorable durability at a current density of 10 mA cm^?2, even surpassing the Pt/C || RuO₂-based EWS (1.60 V). Consequently, the proposed suitable methodology here may accelerate the development of Mo-based electrocatalysts in pH-universal non-noble metal materials for energy conversion.     

Microscopic high-speed video observation of oxygen bubble generation behavior and effects of anode electrode shape on OER performance in alkaline water electrolysis

An important difficulty associated with alkaline water electrolysis is the rise in anode overpotential attributable to bubble coverage of the electrode surface. For this study, a system with a high-speed video camera was developed, achieving in-situ observation of bubble generation on an electrode surface, monitoring an area of 1.02 mm² at 6000 frames per second. The relation between polarization curve (current density up to 3.0 A cm^?2) and oxygen bubble generation behavior on nickel electrodes having cylindrical wires and rectangular wires of different sizes (100–300 μm) was clarified. The generated bubbles slide upward, contacting the electrode surface and detaching at the top edge. Observations indicate that small electrodes have short bubble residence time and thin bubble covering layer on the electrode. As a result, the small electrode diameter contributes to smaller overpotential at high current density.     

Synergistic regulation of hydrogen adsorption/desorption via dual interfaces of Cu/Ni/Ni(OH)2 toward efficient hydrogen evolution reaction

Nickel-based catalysts have attracted tremendous attention as alternatives to precious metal-based catalysts for electrocatalytic hydrogen evolution reaction (HER) in virtue of their conspicuous advantages such as abundant reserves and high electrochemical activity. Nevertheless, a great challenge for Ni-based electrocatalyst is that nickel sites possess too strong adsorption for key intermediates H1, which severely suppresses the hydrogen-production activities. Herein, we report a hierarchical architecture Cu/Ni/Ni(OH)₂ consisting of dual interfaces as a high-efficient electrocatalyst for HER. The Cu nanowire backbone could provide geometric spaces for loading plenty of Ni sites and the formed Ni/Cu interface could effectively weakened the adsorption intensity of H1 intermediates on the catalyst surface. Moreover, the H1 adsorption could be further controlled to appropriate states by in-situ formed Ni(OH)₂/Ni interface, which simultaneously promotes water adsorption and activation, thus both Heyrovsky and Volmer steps in HER could be obviously accelerated. Experimental and theoretical results confirm that this interface structure can promote water dissociation and optimize H1 adsorption. Consequently, the Cu/Ni/Ni(OH)₂ electrocatalyst exhibits a low overpotential of 20 mV at 10 mA cm^?2 and an ultralow Tafel slope of 30 mV dec^?1 in 1.0 M KOH, surpassing those of reported transition-metal-based electrocatalysts and even the prevailing commercial Pt/C.     

Structure engineering of amorphous P–CoS hollow electrocatalysts for promoted oxygen evolution reaction

Oxygen evolution reaction (OER) is a key process involved in many energy-related conversion systems. An ideal OER electrocatalyst should possess rich active sites and optimal binding strength with oxygen-containing intermediates. Although numerous endeavors have been devoted to the modification and optimization of transition-metal-based OER electrocatalysts, they are still operated with sluggish kinetics. Herein, an ion-exchange approach is proposed to realize the structure engineering of amorphous P–CoS hollow nanomaterials by utilizing the ZIF-67 nanocubes as the precursors. The precise structure control of the amorphous hollow nanostructure contributes to the large exposure of surface active sites. Moreover, the introduction of phosphorus greatly modifies the electronic structure of CoS₂, which is thus favorable for optimizing the binding energies of oxygenated species. Furthermore, the incorporation of phosphorus may also induce the formation of surface defects to regulate the local electronic structure and surface environment. As a result of this, such P–CoS hollow nanocatalysts display remarkable electrocatalytic activity and durability towards OER, which require an overpotential of 283 mV to afford a current density of 10 mA cm^?2, outperforming commercial RuO₂ catalyst.     

S/Se dual-doping promotes the formation of active Ni/Fe oxyhydroxide for oxygen evolution reaction of (sea)water splitting

Surface reconstruction produces metal oxyhydroxide (1OOH) active sites, and promoting surface reconstruction is essential for the design of OER electrocatalysts. In this paper, we reported that a large amount of active NiFeOOH was generated in-situ on the surface of nickel-iron sulfide selenide, thus exposing more active sites and efficiently catalyzing OER. In 1 M KOH solution, NiFeOOH(S,Se) achieves an ultra-low overpotential of 195 mV at the current density of 10 mA cm^?2, and the Tafel slope is only 31.99 mV dec^?1, showing excellent catalytic performance. When the current density is 100  mA cm^?2, the over-potential of NiFeOOH(S,Se) in KOH + seawater solution is 239 mV, which is almost equivalent to 231 mV in KOH solution. The excellent OER stability of the NiFeOOH(S,Se) catalyst in alkaline electrolytes was confirmed, and the overpotential did not change significantly after 4 days of testing in KOH + seawater solution.     

Anodic corrosion of heteroatom doped graphene oxide supports and its influence on the electrocatalytic oxygen evolution reaction

Transition metal-based electrocatalysts supported on carbon substrates face the challenges of anodic corrosion of carbon during oxygen evolution reaction at high oxidation potential. The role of electrophilic functional groups (carbonyl, pyridinic, thiol, etc.) incorporated in graphene oxide has been studied towards the anodic corrosion resistance. Heteroatom functionalized carbon supports possess modified electronic properties, surface oxygen content, and hydrophilicity, which are crucial in governing electrochemical corrosion in the alkaline oxidative environment. Evidently, electron-withdrawing groups in NGO support (pyridinic, cyano, nitro, etc) and its lower oxygen content impart maximum corrosion resistance and anodic stability in comparison to the other sulfur-doped and co-doped graphene oxide support. In this report, we establish the baseline evaluation of carbon-supported OER electrocatalysts by a systematic analysis of activity and substrate corrosion resistance. The result of this study establishes the role of surface composition of the doped supports while for designing a stable, corrosion-resistant OER electrocatalyst.     

One-step synthesis of Co2P/N-P co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts

Developing inexpensive and efficient electrocatalysts for hydrogen evolution reaction (HER) in both acidic and alkaline mediums is of great significance to the hydrogen energy industry. Hereby, we prepared a mixture of precursors with homogeneous composition by using the chelating ability of soybean protein isolate (C and N source) and phytic acid (dopant and phosphating agent) with cobalt ions, and achieved one-step synthesis and construction of Co₂P/N–P co-doped porous carbon composite by carbonization at 800 °C. The as-synthesized Co₂P/NPPC-800 electrocatalyst exhibits low HER overpotentials of 121 and 125 mV at 10 mA cm^?2 in 0.5 M H₂SO₄ and 1.0 M KOH, which are close to those of the commercial Pt/C catalyst. Additionally, the NPPC substrate surrounding the Co₂P could diminish the corrosion during the HER, and Co₂P/NPPC-800 displays good stability and durability. Furthermore, this work offers a convenient synthesis strategy for phosphide/doped porous carbon composites in other electrochemical energy technologies.     

Facile fabrication of MOF-decorated nickel iron foam for highly efficient oxygen evolution

Metal-organic frameworks (MOFs) have emerged as efficient electrocatalysts due to the features of high specific surface area, rich pore structure and diversified composition. It is still challenging to synthesize self-supporting MOF-based catalysts using simple and low-cost fabrication methods. Herein, we successfully fabricated Ni-doped MIL-53(Fe) supported on nickel-iron foam (Ni-MIL-53(Fe)/NFF) as efficient electrocatalyst. A facile two-step solvothermal method without adding any metal salts was used, which can simplify the fabrication process and reduce the experimental cost. In the fabrication process, the bimetallic Ni-MIL-53(Fe)/NFF was in situ converted from an intermediate NiFe₂O₄/NFF. The obtained material exhibits outstanding electrocatalytic oxygen evolution performance with a low overpotential of 248 mV at 50 mA cm^?2, and a small Tafel slope of 46.4 mV dec^?1. This work sheds light on the simple and efficient preparation of bimetallic MOF-based material, which is promising in electrocatalysts.     

Scalloped nickel/iron vanadium oxide-coated vanadium dioxides based on chemical etching-induced reconstruction strategy for efficient oxygen evolution

Developing highly efficient and stable noble metal-free electrocatalysts with excellent catalytic surface for oxygen evolution reactions (OER) is an essential link for stimulating hydrogen generation from water electrolysis. Herein, the scalloped nickel/iron vanadium oxide coated vanadium dioxide (named as VO₂@NFVO) has been successfully decorated via a urea-induced chemical etching-reconstruction process in the alkaline solution containing Fe²⁺ and Ni²⁺. Corresponding experimental measurements clearly show that favorable chemical etching occurs with the formation of new phases (eg, Ni₃V₂O₈, FeVO₄), which make it expose a large number of active sites and regulate the electron density of the active center, thus thereby dramatically enhancing the electrocatalytic performance by promoting electron transfer and optimizing the adsorption energy of reaction intermediates. Under optimized condition, the obtained VO₂@NFVO delivers excellent activity merely with smaller overpotential of 290 mV at 10 mA cm^?2, outperforming benchmark RuO₂ catalyst in an alkaline solution. Moreover, its superior durability is verified by chronoamperometry testing. This simple etching-reconstruction strategy opens a new avenue for the preparation of vanadium-based electrocatalysts.     

Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting

Searching high-active, stable and abundant bifunctional catalysts to replace noble metals for hydrogen and oxygen evolution reactions (HER and OER) is desired. Herein, petal-like NiCoP sheets were synthesized on carbon paper covered with a 3D nitrogen-doped carbon nanofiber network (NiCoP/CNNCP) by a simple hydrothermal process followed by phosphorization. The HER overpotential in 0.5 M H₂SO₄ and OER overpotential in 1 M KOH of the NiCoP/CNNCP electrode only required 55 mV and 260 mV to drive a current density of 10 mA cm^?2, respectively, which was comparable or even better than most nickel-and cobalt-based phosphide catalysts. The overall water-splitting electrolyzer with an asymmetric electrolyte system assembled using NiCoP/CNNCP as bifunctional electrodes required an extremely low cell voltage of 1.04 V to achieve a current density of 10 mA cm^?2, which was much lower than almost all alkaline electrolysis systems.