Transition‐metal phosphides have stimulated great interest as catalysts to drive the hydrogen evolution reaction (HER), but their use as bifunctional catalytic electrodes that enable efficient ...neutral‐pH water splitting has rarely been achieved. Herein, we report the synthesis of ternary Ni0.1Co0.9P porous nanosheets onto conductive carbon fiber paper that can efficiently and robustly catalyze both the HER and water oxidation in 1 m phosphate buffer (PBS; pH 7) electrolyte under ambient conditions. A water electrolysis cell comprising the Ni0.1Co0.9P electrodes demonstrates remarkable activity and stability for the electrochemical splitting of neutral‐pH water. We attribute this performance to the new ternary Ni0.1Co0.9P structure with porous surfaces and favorable electronic states resulting from the synergistic interplay between nickel and cobalt. Ternary metal phosphides hold promise as efficient and low‐cost catalysts for neutral‐pH water splitting devices.
Sheets and paper: Ternary Ni0.1Co0.9P porous nanosheets anchored onto conductive carbon fiber paper, can be used as a bifunctional catalytic material for driving both water reduction and oxidation reactions efficiently in neutral‐pH electrolyte under ambient conditions.
The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, ...their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co‐precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self‐reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm−2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale‐up production of amorphous metal oxides for high‐performance OER catalysts.
Amorphous NiFeMo oxide (up to 515 g one batch) with homogeneous elemental distribution was synthesized through a facile supersaturated co‐precipitation method. The amorphous NiFeMo oxide undergoes rapid surface self‐reconstruction during OER that forms a metal oxy(hydroxide) active layer with oxygen vacancies, enabling efficient OER catalysis.
A considerable challenge in the conversion of carbon dioxide into useful fuels comes from the activation of CO2 to CO2.− or other intermediates, which often requires precious‐metal catalysts, high ...overpotentials, and/or electrolyte additives (e.g., ionic liquids). We report a microwave heating strategy for synthesizing a transition‐metal chalcogenide nanostructure that efficiently catalyzes CO2 electroreduction to carbon monoxide (CO). We found that the cadmium sulfide (CdS) nanoneedle arrays exhibit an unprecedented current density of 212 mA cm−2 with 95.5±4.0 % CO Faraday efficiency at −1.2 V versus a reversible hydrogen electrode (RHE; without iR correction). Experimental and computational studies show that the high‐curvature CdS nanostructured catalyst has a pronounced proximity effect which gives rise to large electric field enhancement, which can concentrate alkali‐metal cations resulting in the enhanced CO2 electroreduction efficiency.
The needle has landed: CdS nanostructures with sharp tips can generate large electric fields that lead to increased CO2 concentrations for CO2‐to‐CO conversion. The localized electric fields are significantly enhanced when two nanoneedles are in close proximity. These advantages result in CO2 electrocatalytic reduction with a 95.5±4.0 % CO Faraday efficiency.
Operating fuel cells in alkaline environments permits the use of platinum-group-metal-free (PGM-free) catalysts and inexpensive bipolar plates, leading to significant cost reduction. Of the PGM-free ...catalysts explored, however, only a few nickel-based materials are active for catalyzing the hydrogen oxidation reaction (HOR) in alkali; moreover, these catalysts deactivate rapidly at high anode potentials owing to nickel hydroxide formation. Here we describe that a nickel-tungsten-copper (Ni
WCu
) ternary alloy showing HOR activity rivals Pt/C benchmark in alkaline electrolyte. Importantly, we achieved a high anode potential up to 0.3 V versus reversible hydrogen electrode on this catalyst with good operational stability over 20 h. The catalyst also displays excellent CO-tolerant ability that Pt/C catalyst lacks. Experimental and theoretical studies uncover that nickel, tungsten, and copper play in synergy to create a favorable alloying surface for optimized hydrogen and hydroxyl bindings, as well as for the improved oxidation resistance, which result in the HOR enhancement.
The incorporation of defects, such as vacancies, into functional materials could substantially tailor their intrinsic properties. Progress in vacancy chemistry has enabled advances in many ...technological applications, but creating new type of vacancies in existing material system remains a big challenge. We show here that ionized nitrogen plasma can break bonds of iron-carbon-nitrogen-nickel units in nickel-iron Prussian blue analogues, forming unconventional carbon-nitrogen vacancies. We study oxygen evolution reaction on the carbon-nitrogen vacancy-mediated Prussian blue analogues, which exhibit a low overpotential of 283 millivolts at 10 milliamperes per square centimeter in alkali, far exceeding that of original Prussian blue analogues and previously reported oxygen evolution catalysts with vacancies. We ascribe this enhancement to the in-situ generated nickel-iron oxy(hydroxide) active layer during oxygen evolution reaction, where the Fe leaching was significantly suppressed by the unconventional carbon-nitrogen vacancies. This work opens up opportunities for producing vacancy defects in nanomaterials for broad applications.
Selective and efficient catalytic conversion of carbon dioxide (CO2) into value-added fuels and feedstocks provides an ideal avenue to high-density renewable energy storage. An impediment to enabling ...deep CO2 reduction to oxygenates and hydrocarbons (e.g., C2+ compounds) is the difficulty of coupling carbon–carbon bonds efficiently. Copper in the +1 oxidation state has been thought to be active for catalyzing C2+ formation, whereas it is prone to being reduced to Cu0 at cathodic potentials. Here we report that catalysts with nanocavities can confine carbon intermediates formed in situ, which in turn covers the local catalyst surface and thereby stabilizes Cu+ species. Experimental measurements on multihollow cuprous oxide catalyst exhibit a C2+ Faradaic efficiency of 75.2 ± 2.7% at a C2+ partial current density of 267 ± 13 mA cm–2 and a large C2+-to-C1 ratio of ∼7.2. Operando Raman spectra, in conjunction with X-ray absorption studies, confirm that Cu+ species in the as-designed catalyst are well retained during CO2 reduction, which leads to the marked C2+ selectivity at a large conversion rate.
Electrosynthesis of hydrogen peroxide (H2O2) in the acidic environment could largely prevent its decomposition to water, but efficient catalysts that constitute entirely earth‐abundant elements are ...lacking. Here we report the experimental demonstration of narrowing the interlayer gap of metallic cobalt diselenide (CoSe2), which creates high‐performance catalyst to selectively drive two‐electron oxygen reduction toward H2O2 in an acidic electrolyte. The enhancement of the interlayer coupling between CoSe2 atomic layers offers a favorable surface electronic structure that weakens the critical *OOH adsorption, promoting the energetics for H2O2 production. Consequently, on the strongly coupled CoSe2 catalyst, we achieved Faradaic efficiency of 96.7 %, current density of 50.04 milliamperes per square centimeter, and product rate of 30.60 mg cm−2 h−1. Moreover, this catalyst shows no sign of degradation when operating at −63 milliamperes per square centimeter over 100 hours.
A strategy that narrows the interlayer distance of cobalt diselenide (CoSe2) is reported, which enables strong coupling between CoSe2 monolayers. The strongly coupled CoSe2 can catalyze electrosynthesis of H2O2 in acidic media efficiently, which yields Faradaic efficiency of 96.7 %, current density of 50.04 mA cm−2, and product rate of 30.60 mg cm−2 h−1, outperforming all catalysts reported previously in acidic environments.
Although the Turing structures, or stationary reaction‐diffusion patterns, have received increasing attention in biology and chemistry, making such unusual patterns on inorganic solids is ...fundamentally challenging. We report a simple cation exchange approach to produce Turing‐type Ag2Se on CoSe2 nanobelts relied on diffusion‐driven instability. The resultant Turing‐type Ag2Se‐CoSe2 material is highly effective to catalyze the oxygen evolution reaction (OER) in alkaline electrolytes with an 84.5 % anodic energy efficiency. Electrochemical measurements show that the intrinsic OER activity correlates linearly with the length of Ag2Se‐CoSe2 interfaces, determining that such Turing‐type interfaces are more active sites for OER. Combing X‐ray absorption and computational simulations, we ascribe the excellent OER performance to the optimized adsorption energies for critical oxygen‐containing intermediates at the unconventional interfaces.
A novel Turing‐type Ag2Se‐CoSe2 structure has been synthesized, which possesses rich Ag2Se‐CoSe2 interfaces, exhibiting a 221 mV overpotential at a current density of 10 mA cm−2 in 0.1 M KOH electrolyte with a high anodic energy efficiency of 84.5 %.
Hydroxide exchange membrane fuel cells offer possibility of adopting platinum-group-metal-free catalysts to negotiate sluggish oxygen reduction reaction. Unfortunately, the ultrafast hydrogen ...oxidation reaction (HOR) on platinum decreases at least two orders of magnitude by switching the electrolytes from acid to base, causing high platinum-group-metal loadings. Here we show that a nickel-molybdenum nanoalloy with tetragonal MoNi
phase can catalyze the HOR efficiently in alkaline electrolytes. The catalyst exhibits a high apparent exchange current density of 3.41 milliamperes per square centimeter and operates very stable, which is 1.4 times higher than that of state-of-the-art Pt/C catalyst. With this catalyst, we further demonstrate the capability to tolerate carbon monoxide poisoning. Marked HOR activity was also observed on similarly designed WNi
catalyst. We attribute this remarkable HOR reactivity to an alloy effect that enables optimum adsorption of hydrogen on nickel and hydroxyl on molybdenum (tungsten), which synergistically promotes the Volmer reaction.
Many platinum group metal-free inorganic catalysts have demonstrated high intrinsic activity for diverse important electrode reactions, but their practical use often suffers from undesirable ...structural degradation and hence poor stability, especially in acidic media. We report here an alkali-heating synthesis to achieve phase-mixed cobalt diselenide material with nearly homogeneous distribution of cubic and orthorhombic phases. Using water electroreduction as a model reaction, we observe that the phase-mixed cobalt diselenide reaches the current density of 10 milliamperes per square centimeter at overpotential of mere 124 millivolts in acidic electrolyte. The catalyst shows no sign of deactivation after more than 400 h of continuous operation and the polarization curve is well retained after 50,000 potential cycles. Experimental and computational investigations uncover a boosted covalency between Co and Se atoms resulting from the phase mixture, which substantially enhances the lattice robustness and thereby the material stability. The findings provide promising design strategy for long-lived catalysts in acid through crystal phase engineering.
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