Superior hydrogen evolution electrocatalysis enabled by CoP nanowire array on graphite felt

Renewable electricity-powered hydrogen production is an attractive alternative to unsustainable industrial processes, but the large-scale implantation of such sustainable technology still requires efficient and noble-metal-free electrocatalysts for driving cathodic hydrogen evolution reaction (HER), especially under alkaline conditions. In this paper, CoP nanowire array was in-situ developed on porous graphite felt (CoP/GF) as a new 3D electrocatalyst in facilitating hydrogen evolution electrocatalysis. This CoP/GF presents outstanding HER activity, requiring a low overpotential of 130 mV to deliver a current density of 20 mA cm^?2 as tested in 1.0 M KOH. Furthermore, this free-standing catalyst exhibits impressive long-term durability of up to 50 h under working conditions.     

PH-induced structural evolution,photodegradation mechanism and application of bismuth molybdate photocatalyst

In this work, we have elucidated the pH-induced structural evolution of bismuth molybdate photocatalyst based on a hydrothermal synthesis route. With increasing the pH value of precursor solution, pure Bi₂MoO₆ was synthesized at pH 2–5, Bi₂MoO₆-Bi₄MoO₉ mixture was obtained at pH 7–9, pure Bi₄MoO₉ was obtained at pH 11, and pure α-Bi₂O₃ was derived at pH 13. The as-derived samples mainly present particle-like shapes but with different particle sizes (except the observation of Bi₂MoO₆ nanowires in sample S-pH9). The photocatalytic performances between the samples were compared via the degradation of methylene blue (MB) under irradiation of simulated sunlight. The Bi₂MoO₆ sample synthesized at pH 2 exhibited the highest photodegradation performance (η(30 min) = 89.8 %, k_app = 0.05007 min^?1) among the samples. The underlying photocatalytic mechanism and degradation pathways of MB were systematically analyzed. Moreover, the photodegradation performance of the Bi₂MoO₆ photocatalyst was further evaluated at different acidic-alkaline environments as well as in degrading various color and colorless organic pollutants, which provides an important insight into its practical application.     

Nitrogen-doped cobalt sulfide as an efficient electrocatalyst for hydrogen evolution reaction in alkaline and acidic media

The enhancement in intrinsic catalytic activity and material conductivity of an electrocatalyst can leads to promoting HER activity. Herein, a successful nitrogenation of CoS₂ (N–CoS₂) catalyst has been investigated through the facile hydrothermal process followed by N₂ annealing treatment. An optimized N–CoS₂ catalyst reveals an outstanding hydrogen evolution reaction (HER) performance in alkaline as well as acidic electrolyte media, exhibiting an infinitesimal overpotential of ?0.137 and ?0.097 V at a current density of ?10 mA/cm² (?0.309 and ?0.275 V at ?300 mA/cm²), corresponding respectively, with a modest Tafel slope of 117 and 101 mV/dec. Moreover, a static voltage response was observed at low and high current rates (?10 to ?100 mA/cm²) along with an excellent endurance up to 50 h even at ?100 mA/cm². The excellent catalytic HER performance is ascribed to improved electronic conductivity and enhanced electrochemically active sites, which is aroused from the synergy and mutual interaction between heteroatoms that might have varied the surface chemistry of an active catalyst.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

Highly stable γ-NiOOH/ZnCdS photocatalyst for efficient hydrogen evolution

It is extremely desirable to develop high hydrogen evolution activity and stable visible-light-driven photocatalysts. The sluggish oxidation process and holes accumulation are the main obstacles to high catalysis activity and photo-stability. An efficient γ-NiOOH/ZnCdS photocatalyst was prepared by in-situ hydrothermal method. The γ-NiOOH nanosheets distribute on ZnCdS nanospheres surface and accelerate holes transfer. The hydrogen evolution rate is up to 48.60 mmol g^?1 h^?1 under visible-light illumination (λ = 400–780 nm), about 10.8 times of pure ZnCdS (4.50 mmol g^?1 h^?1) and 1.8 times of general β-NiOOH modified ZnCdS (27.40 mmol g^?1 h^?1). And apparent quantum yield of γ-NiOOH/ZCS-100 is up to 18.23% (400 nm). The carrier lifetime extends from 5.50 ns (ZnCdS) to 6.10 ns (γ-NiOOH/ZCS), examined by steady photoluminescence and time-resolved photoluminescence. Moreover, the γ-NiOOH/ZCS photocatalyst has exhibited excellent photo-stability even after one-year of storage. The γ-NiOOH nanosheets can be an excellent co-catalyst on accelerating both holes transfer and oxidation process for high photo-stability and photo-activity.     

Enhanced oxygen evolution reaction kinetics through biochar-based nickel-iron phosphides nanocages in water electrolysis for hydrogen production

Highly-efficient and stable non-noble metal electrocatalysts for overcoming the sluggish kinetics of oxygen evolution reaction (OER) is urgent for water electrolysis. Biomass-derived biochar has been considered as promising carbon material because of its advantages such as low-cost, renewable, simple preparation, rich structure, and easy to obtain heteroatom by in-situ doping. Herein, Ni₂P–Fe₂P bimetallic phosphide spherical nanocages encapsulated in N/P-doped pine needles biochar is prepared via a simple two-step pyrolysis method. Benefiting from the maximum synergistic effects of bimetallic phosphide and biochar, high conductivity of biochar encapsulation, highly exposed active sites of Ni₂P–Fe₂P spherical nanocages, rapid mass transfer in porous channels with large specific surface area, and the promotion in adsorption of reaction intermediates by high-level heteroatom doping, the (Ni_0.75Fe_0.25)₂P@NP/C demonstrates excellent OER activity with an overpotential of 250 mV and a Tafel slope of 48 mV/dec at 10 mA/cm² in 1 M KOH. Also it exhibits a long-term durability in 10 h electrolysis and its activity even improves during the electrocatalytic process. The present work provides a favorable strategy for the inexpensive synthesis of biochar-based transition metal electrocatalysts toward OER, and improves the water electrolysis for hydrogen production.     

Parameter characterization of HTPEMFC using numerical simulation and genetic algorithms

This paper develops a novel approach to the parameterisation of high temperature exchange membrane fuel cells (HTPEMFC) with limited and non-invasive measurements. The proposed method allows an effective identification of electrochemical parameters for three-dimensional fuel cell models by combining computational simulation tools and genetic algorithms. To avoid each evaluation undertaken by the optimisation method involving a complete computational simulation of the 3D model, a strategy has been designed that, thanks to an iterative process, makes it possible to decouple the fluid dynamic resolution from the electrochemistry one.Two electrochemical models have been incorporated into these tools to describe the behaviour of the catalyst layer, Butler-Volmer and spherical aggregate. For each one, a case study has been carried out to validate the results by comparing them with empirical data in the first model and with data generated by numerical simulation in the second. Results show that, from a set of measured operating conditions, it is possible to identify a unique set of electrochemical parameters that fits the 3D model to the target polarisation curve. The extension of this framework can be used to systematically estimate any model parameter in order to reduce the uncertainty in 3D simulation predictions.     

Hydrangea like composite catalysts of ultrathin Mo2S3 nanosheets assembled on N,S-dual-doped graphitic biocarbon spheres with highly electrocatalytic activity for HER

Water electrolysis is the most clean and high-efficiency technology for production of hydrogen, an ultimate clean energy in future. Highly efficient non-noble electrocatalysts for hydrogen evolution reaction (HER) are desirable for large scale production of hydrogen by water electrolysis. Especially, exposing as many active sites as possible is a vital way to improve activities of the catalysts. Herein, a series of new hydrangea like composite catalysts of ultrathin Mo₂S₃ nanosheets assembled uprightly and interlacedly on N, S-dual-doped graphitic biocarbon spheres were facilely prepared. The unique structure endowed the catalysts highly exposed edge active sites and prominently high activities for HER. Especially, the optimized catalyst Mo₂S₃/NSCS-50 exhibited as low as 106 mV of overpotential at 10 mA/cm² (denoted as ?₁₀). The catalyst also showed low Tafel slope of 53 mV/dec, low electron transfer resistance of 34 Ω and high stability evidenced by the result that the current density only attenuated 11.7% after 10 h i-t test. The catalyst has shown broad prospect for commercial application in water electrolysis.     

K–I co-doped crystalline carbon nitride with outstanding visible light photocatalytic activity for H2 evolution

Heteroatomic doping is an effective way to optimize the electronic structure of carbon nitride to boost photocatalytic performance. However, the extra introduced defects could result in the decrease of its crystallinity. In this work, crystalline K–I co-doped carbon nitride (K–I–CCN) was simply synthesized from molten salt ionthermal post-calcination in nitrogen atmosphere. Structure characterization results indicate that compared to K–CCN synthesized from conventional molten salt heat treatment in air, nitrogen heating atmosphere is more conductive for the formation of homogeneous pore structure of the catalyst, which has larger surface area and pore volume, while could repairing some defects and resulting in better polymerization crystallization. In addition, except the implanting of K, I doping is still retained after nitrogen heat treatment, thus forming K–I co-doping structure. Due to the positive charge effect of K–I co-doping, K–I–CCN has a narrower band gap, higher surface charge density and stronger charge transport, so it performs significantly enhanced photocatalytic H₂ evolution activity from water splitting.