Bimetallic nickel-molybdenum/tungsten nanoalloys for high-efficiency hydrogen oxidation catalysis in alkaline electrolytes.
ABSTRACT: 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 MoNi4 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 WNi4 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.
Project description: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<sub>5.2</sub>WCu<sub>2.2</sub>) 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.
Project description:Chemical vapor phase deposition was used to create hydrophobic nanostructured surfaces on glass slides. Subsequently, hydrophilic channels were created by sputtering a metal catalyst on the channels while masking the outside. The surface tension gradient between the hydrophilic surface in the channels and the outside hydrophobicity formed the open-channel system. The reduction of <i>para-</i>nitrophenol (PNP) was studied on these devices. When compared to nanostructure-free reference systems, the created nanostructures, namely, silicone nanofilaments (SNFs) and nano-bagels, had superior catalytic performance (73% and 66% conversion to 55% at 0.5 µL/s flow rate using 20 nm platinum) and wall integrity; therefore, they could be readily used multiple times. The created nanostructures were stable under the reaction conditions, as observed with scanning electron microscopy. Transition electron microscopy studies of platinum-modified SNFs revealed that the catalyst is present as nanoparticles ranging up to 13 nm in size. By changing the target in the sputter coating unit, molybdenum, gold, nickel and copper were evaluated for their catalytic efficiency. The relative order was platinum < gold = molybdenum < nickel < copper. The decomposition of sodium borohydride (NaBH<sub>4</sub>) by platinum as a concurrent reaction to the <i>para</i>-nitrophenol reduction terminates the reaction before completion, despite a large excess of reducing agent. Gold had the same catalytic rate as molybdenum, while nickel was two times and copper about four times faster than gold. In all cases, there was a clear improvement in catalysis of silicone nanofilaments compared to a flat reference system.
Project description:Efficient heterogeneous catalysis of hydrogen oxidation reaction (HOR) by platinum group metal (PGM)-free catalysts in proton-exchange membrane (PEM) fuel cells represents a significant challenge toward the development of a sustainable hydrogen economy. Here, we show that graphene acid (GA) can be used as an electrode scaffold for the noncovalent immobilization of a bioinspired nickel bis-diphosphine HOR catalyst. The highly functionalized structure of this material and optimization of the electrode-catalyst assembly sets new benchmark electrocatalytic performances for heterogeneous molecular HOR, with current densities above 30 mA cm-2 at 0.4 V versus reversible hydrogen electrode in acidic aqueous conditions and at room temperature. This study also shows the great potential of GA for catalyst loading improvement and porosity management within nanostructured electrodes toward achieving high current densities with a noble-metal free molecular catalyst.
Project description:Most photoanodes commonly applied in solar fuel research (e.g., of Fe<sub>2</sub>O<sub>3</sub>, BiVO<sub>4</sub>, TiO<sub>2</sub>, or WO<sub>3</sub>) are only active and stable in alkaline electrolytes. Silicon (Si)-based photocathodes on the other hand are mainly studied under acidic conditions due to their instability in alkaline electrolytes. Here, we show that the in-diffusion of nickel into a 3D Si structure, upon thermal annealing, yields a thin (sub-100 nm), defect-free nickel silicide (NiSi) layer. This has allowed us to design and fabricate a Si microwire photocathode with a NiSi interlayer between the catalyst and the Si microwires. Upon electrodeposition of the catalyst (here, nickel molybdenum) on top of the NiSi layer, an efficient, Si-based photocathode was obtained that is stable in strongly alkaline solutions (1 M KOH). The best-performing, all-earth-abundant microwire array devices exhibited, under AM 1.5G simulated solar illumination, an ideal regenerative cell efficiency of 10.1%.
Project description:Efficient electrocatalyst toward hydrogen evolution/oxidation reactions (HER/HOR) and oxygen reduction reaction (ORR) is desirable for water splitting, fuel cells, etc. Herein, we report an advanced platinum phosphide (PtP<sub>2</sub>) material with only 3.5 wt % Pt loading embedded in phosphorus and nitrogen dual-doped carbon (PNC) layer (PtP<sub>2</sub>@PNC). The obtained catalyst exhibits robust HER, HOR, and ORR performance. For the HER, a much low overpotential of 8 mV is required to achieve the current density of 10 mA cm<sup>-2</sup> compared with Pt/C (22 mV). For the HOR, its mass activity (MA) at an overpotential of 40 mV is 2.3-fold over that of the Pt/C catalyst. Interestingly, PtP<sub>2</sub>@PNC also shows exceptional ORR MA which is 2.6 times higher than that of Pt/C and has robust stability in alkaline solutions. Undoubtedly, this work reveals that PtP<sub>2</sub>@PNC can be employed as nanocatalysts with an impressive catalytic activity and stability for broad applications in electrocatalysis.
Project description:Molybdenum disulfide (MoS2)-based materials have been recently identified as promising electrocatalysts for hydrogen evolution reaction (HER). However, little work has been done to improve the catalytic performance of MoS2 toward HER in alkaline electrolytes, which is more suitable for water splitting in large-scale applications. Here, it is reported that the hybridization of 0D nickel hydr(oxy)oxide nanoparticles with 2D metallic MoS2 nanosheets can significantly enhance the HER activities in alkaline and neutral electrolytes. Impressively, the optimized hybrid catalyst can drive a cathodic current density of 10 mA cm-2 at an overpotential of ≈73 mV for HER in 1 m KOH, about 185 mV smaller than the original MoS2. The improved HER activity is attributed to a bifunctional mechanism adopted in these hybrid catalysts, in which nickel hydr(oxy)oxide promotes the water adsorption and dissociation to supply protons for subsequent reactions occurred on MoS2 to generate H2.
Project description:The low activity of the oxygen reduction reaction in polymer electrolyte membrane fuel cells is a major barrier for electrocatalysis, and hence needs to be optimized. Tuning the surface electronic structure of platinum-based bimetallic alloys, a promising oxygen reduction reaction catalyst, plays a key role in controlling its interaction with reactants, and thus affects the efficiency. Here we report that a dealloying process can be utilized to experimentally fabricate the interface between dealloyed platinum-nickel alloy and amorphous nickel boride membrane. The coating membrane works as an electron acceptor to tune the surface electronic structure of the platinum-nickel catalyst, and this composite catalyst composed of crystalline platinum-nickel covered by amorphous nickel boride achieves a 27-times enhancement in mass activity relative to commercial platinum/carbon at 0.9?V for the oxygen reduction reaction performance. Moreover, this interactional effect between a crystalline surface and amorphous membrane can be readily generalized to facilitate the 3-times higher catalytic activity of commercial platinum/carbon.
Project description:With the massive consumption of fossil fuels and its detrimental impact on the environment, methods of generating clean power are urgent. Hydrogen is an ideal carrier for renewable energy; however, hydrogen generation is inefficient because of the lack of robust catalysts that are substantially cheaper than platinum. Therefore, robust and durable earth-abundant and cost-effective catalysts are desirable for hydrogen generation from water splitting via hydrogen evolution reaction. Here we report an active and durable earth-abundant transition metal dichalcogenide-based hybrid catalyst that exhibits high hydrogen evolution activity approaching the state-of-the-art platinum catalysts, and superior to those of most transition metal dichalcogenides (molybdenum sulfide, cobalt diselenide and so on). Our material is fabricated by growing ternary molybdenum sulfoselenide particles on self-standing porous nickel diselenide foam. This advance provides a different pathway to design cheap, efficient and sizable hydrogen-evolving electrode by simultaneously tuning the number of catalytic edge sites, porosity, heteroatom doping and electrical conductivity.
Project description:The effect of the nature of the catalyst on the performance and mechanism of the hydrogen oxidation reaction (HOR) is discussed for the first time in this work. HOR is an anodic reaction that takes place in anionic exchange membrane fuel cells (AEMFCs) and hydrogen pumps (HPs). Among the investigated catalysts, Pt exhibited the best performance in the HOR. However, the cost and the availability limit the usage. Co is incorporated as a co-catalyst due to its oxophylic nature. Five different PtCo catalysts with different Pt loading values were synthesized in order to decrease Pt loading. The catalytic activities and the reaction mechanism were studied via electrochemical techniques, and it was found that both features are a function of Pt loading; low-Pt-loading catalysts (Pt loading < 2.7%) led to a high half-wave potential in the hydrogen oxidation reaction, which is related to higher activation energy and an intermediate Tafel slope value, related to a mixed HOR mechanism. However, catalysts with moderate Pt loading (Pt loading > 3.1%) exhibited lower E<sub>1/2</sub> than the other catalysts and exhibited a mechanism similar to that of commercial Pt catalysts. Our results demonstrate that Co plays an active role in the HOR, facilitating H<sub>ads</sub> desorption, which is the rate-determining step (RDS) in the mechanism of the HOR.
Project description:The latest progress in alkaline anion-exchange membranes has led to the expectation that less costly catalysts than those of the platinum-group metals may be used in anion-exchange membrane fuel cell devices. In this work, we compare structural properties and the catalytic activity for the hydrogen-oxidation reaction (HOR) for carbon-supported nanoparticles of Ni, Ni<sub>3</sub>Co, Ni<sub>3</sub>Cu, and Ni<sub>3</sub>Fe, synthesized by chemical and solvothermal reduction of metal precursors. The catalysts are well dispersed on the carbon support, with particle diameter in the order of 10 nm, and covered by a layer of oxides and hydroxides. The activity for the HOR was assessed by voltammetry in hydrogen-saturated aqueous solutions of 0.1 mol dm<sup>-1</sup> KOH. A substantial activation by potential cycling of the pristine catalysts synthesized by solvothermal reduction is necessary before these become active for the HOR; in situ Raman spectroscopy shows that after activation the surface of the Ni/C, Ni<sub>3</sub>Fe, and Ni<sub>3</sub>Co catalysts is fully reduced at 0 V, whereas the surface of the Ni<sub>3</sub>Cu catalyst is not. The activation procedure had a smaller but negative impact on the catalysts synthesized by chemical reduction. After activation, the exchange-current densities normalized with respect to the ECSA (electrochemically active surface area) were approximately independent of composition but relatively high compared to catalysts of larger particle diameter.