Introducing defects and in situ topotactic transformation of the electrocatalysts generating heterostructures of mixed‐metal oxides(hydroxides) that are highly active for oxygen evolution reaction (OER) in tandem with metals of low hydrogen adsorption barrier for efficient hydrogen evolution reaction (HER) is urgently demanded for boosting the sluggish OER and HER kinetics in alkaline media. Ascertaining that, metal–organic‐framework‐derived freestanding, defect‐rich, and in situ oxidized Fe–Co–O/Co metal@N‐doped carbon (Co@NC) mesoporous nanosheet (mNS) heterostructure on Ni foam (Fe–Co–O/Co@NC‐mNS/NF) is developed from the in situ oxidation of micropillar‐like heterostructured Fe–Co–O/Co@NC/NF precatalyst. The in situ oxidized Fe–Co–O/Co@NC‐mNS/NF exhibits excellent bifunctional properties by demanding only low overpotentials of 257 and 112 mV, respectively, for OER and HER at the current density of 10 mA cm−2, with long‐term durability, attributed to the existence of oxygen vacancies, higher specific surface area, increased electrochemical active surface area, and in situ generated new metal (oxyhydr)oxide phases. Further, Fe–Co–O/Co@NC‐mNS/NF (+/−) electrolyzer requires only a low cell potential of 1.58 V to derive a current density of 10 mA cm−2. Thus, the present work opens a new window for boosting the overall alkaline water splitting.
Large-scale
H2 production from water by electrochemical
water-splitting is mainly limited by the sluggish kinetics of the
nonprecious-based anode catalysts for oxygen evolution reaction (OER).
Here, we report layer-by-layer in situ growth of low-level Fe-doped
Ni-layered double hydroxide (Ni1–x
Fe
x
-LDH) and Co-layered double hydroxide
(Co1–x
Fe
x
-LDH), respectively, with three-dimensional microflower and one-dimensional
nanopaddy-like morphologies on Ni foam, by a one-step eco-friendly
hydrothermal route. In this work, an interesting finding is that both
Ni1–x
Fe
x
-LDH and Co1–x
Fe
x
-LDH materials are very active and efficient for OER as
well as hydrogen evolution reaction (HER) catalytic activities in
alkaline medium. The electrochemical studies demonstrate that Co1–x
Fe
x
-LDH
material exhibits very low OER and HER overpotentials of 249 and 273
mV, respectively, at a high current density of 50 mA cm–2, whereas Ni1–x
Fe
x
-LDH exhibits 297 and 319 mV. To study the overall
water-splitting performance using these electrocatalysts as anode
and cathode, three types of alkaline electrolyzers are fabricated,
namely, Co1–x
Fe
x
-LDH(+)∥Co1–x
Fe
x
-LDH(−), Ni1–x
Fe
x
-LDH(+)∥Ni1–x
Fe
x
-LDH(−), and
Co1–x
Fe
x
-LDH(+)∥Ni1–x
Fe
x
-LDH(−). These electrolyzers require
only a cell potential (E
cell) of 1.60,
1.60, and 1.59 V, respectively, to drive the benchmark current density
of 10 mA cm–2. Another interesting finding is that
their catalytic activities are enhanced after stability tests. Systematic
analyses are carried out on both electrodes after all electrocatalytic
activity studies. The developed three types of electrolyzers to produce
H2, are very efficient, cost-effective, and offer no complications
in synthesis of materials and fabrication of electrolyzers, which
can greatly enable the realization of clean renewable energy infrastructure.
Hollow‐structured FexCo2−xP, FexCo3−xO4, and Prussian blue analogue (FeCo‐PBA) microbuilding arrays on Ni foam (NF) are derived from Co‐based metal–organic frameworks (Co‐MOF) using a simple room temperature and post‐heat‐treatment route. Among them, FexCo2−xP/NF shows excellent bifunctional catalytic activities by demonstrating very low oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) overpotentials of 255/114 mV at a current density of 20/10 mA cm−2 respectively, whereas FexCo3−xO4/NF and FeCo‐PBA/NF demand higher overpotentials. Remarkably, for water electrolysis, FexCo2−xP/NF requires only 1.61 V to obtain 10 mA cm−2. In contrast to water electrolysis, urea electrolysis reduces overpotential and simultaneously purifies the urea‐rich wastewater. The urea oxidation reaction at the FexCo2−xP/NF anode needs just 1.345 V to achieve 20 mA cm−2, which is 140 mV less than the 1.48 V potential required for OER. Moreover, the generation of H2 through urea electrolysis needs only 1.42 V to drive 10 mA cm−2.
Electrocatalytic water-splitting performance of MoS2 nanostructures can be improved by increasing edge density, activating basal planes, expanding interlayer spacing and stabilizing the 1T-phase. In this work, for the first time,...
Introducing amorphous and ultrathin nanosheets of transition bimetal phosphate arrays that are highly active in the oxygen evolution reaction (OER) as shells over an electronically modulated crystalline core with low hydrogen absorption energy for an excellent hydrogen evolution reaction (HER) can boost the sluggish kinetics of the OER and HER in alkaline electrolytes. Therefore, in this study, ultrathin and amorphous cobalt‐nickel‐phosphate (CoNiPO
x
) nanosheet arrays are deposited over vanadium (V)‐doped cobalt‐nitride (V
3%
‐Co
4
N) crystalline core nanowires to obtain amorphous‐shell@crystalline‐core mesoporous 3D‐heterostructures (CoNiPO
x
@V‐Co
4
N/NF) as bifunctional electrocatalysts. The optimized electrocatalyst shows extremely low HER and OER overpotentials of 53 and 270 mV at 10 mA cm
−2
, respectively. The CoNiPO
x
@V
3%
‐Co
4
N/NF (+/−) electrolyzer utilizing the electrocatalyst as both anode and cathode demonstrates remarkable overall water‐splitting activity, requiring a cell potential of only 1.52 V at 10 mA cm
−2
, 30 mV lower than that of the RuO
2
/NF (+)/20%‐Pt/C/NF (−) electrolyzer. Such impressive bifunctional activities can be attributed to abundant active sites, adjusted electronic structure, lower charge‐transfer resistance, enhanced electrochemically active surface area (ECSA), and surface‐ and volume‐confined electrocatalysis resulting from the synergistic effects of the crystalline V
3%
‐Co
4
N core and amorphous CoNiPO
x
shells boosting water splitting in alkaline media.
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