Growth of Ni/Mo/Cu on carbon fiber paper: An efficient electrocatalyst for hydrogen evolution reaction

The exploration of efficient catalysts toward hydrogen evolution reaction (HER) is still an urgent task. In this paper, Ni/Mo/Cu/C and Ni/Mo/C electrode were obtained by conventional pulse voltammetry, which acted as cathode in microbial electrolysis cells (MECs). The prepared samples are analyzed using SEM, XRD, XPS and electrochemical analysis techniques. Results indicated that the Ni/Mo/Cu coating has a rough and globular structure and presents high current density, a lower Tafel slope of 23.9 mV/dec than 30 mV/dec of Pt, which exceeds the electrochemical activity of Pt electrode. Its remarkably enhanced electrocatalytic activity is attributed to the high surface area, high conductivity as well as synergistic interaction among Ni, Mo and Cu.     

Recent advances in two-dimensional Pt based electrocatalysts for methanol oxidation reaction

Direct methanol fuel cells (DMFCs) had been attracted considerable attention for its advantages of high energy density, simplified systems and readily transportation and storage of methanol. However, the notoriously sluggish kinetics of methanol oxidation reaction (MOR) of the anode reaction, had greatly affected the commercialization of DMFCs. On one hand, Pt based catalyst are still the most effective MOR catalysts, while the high cost caused by the high loadings of electrocatalyst to compensate the low MOR activity impedes the wide accessible of DMFCs. In addition, the occurrence of catalyst poisoning owing to the strong interaction between Pt and carbon monoxide (CO) generated during the MOR processing, further leading to the fast decay in the performance and stability of MOR electrocatalysts. Two-dimensional (2D) Pt based nanostructures is regarded to be one promising and effective class of MOR electrocatalysts, and attracted much attention due to the high electron mobility, highly exposed active sites, and extraordinary thermal conduction. In this review, the mechanism of MOR was firstly introduced, and then the synthesis conditions, structure characteristics and methanol oxidation performances both in acidic and alkaline dielectric of 2D Pt based nanocatalysts were introduced. Subsequently, we briefly analyzed the structural characteristics of 2D Pt based nanocatalysts and their advantages, including the low platinum loadings, high specific surface area and majority of atomic active sites exposed. Finally, the opportunities and challenges for designing of advanced 2D Pt based nanocatalysts was proposed and discussed.     

Highly dispersed MnO nanoparticles supported on N-doped rGO as an efficient oxygen reduction electrocatalyst via high-temperature pyrolysis

Transition metal-based compounds, due to their excellent ORR catalytic performance under alkaline condition, have recently emerged as one of the most promising alternatives to noble metal-based ORR catalysts. It is worth noting that manganese oxide can take an unique advantage for decomposition of intermediate adsorption products H₂O₂ and can effectively reduce O₂ to OH⁻. However, most research has focused on MnO₂, while attention has rarely been paid to MnO catalysts. In addition, under high-temperature pyrolysis condition, MnO is the most stable manganese oxide but MnO nanoparticles easily agglomerate. Hence, it is very difficult to obtain well-dispersed and small-sized MnO nanoparticles. Herein, on the basis of pre-synthesizing uniformly distributed manganese complexes on the reduced graphene oxide (rGO), we innovatively prepare highly dispersed and small-sized MnO nanoparticles (~3.94 nm) via high-temperature pyrolysis, which are uniformly anchored on N-doped reduced graphene oxide (NrGO) as an efficient oxygen reduction electrocatalyst. The as-obtained MnO/NrGO (1050 °C) electrocatalyst achieves satisfactory onset potential (0.942 V) and half-wave potential (0.820 V) under alkaline condition. And the limiting current density is 4.17 mA cm⁻², which is very close to that of Pt/C (20 wt%, JM). Meanwhile, MnO/NrGO (1050 °C) catalyst presents superior longstanding durability and methanol resistance than Pt/C (JM). This work indicates that high-temperature pyrolysis can improve the purity of manganese oxide, simultaneously the defects of NrGO can reduce particle size of MnO nanoparticles, which are greatly beneficial to improve ORR performance. This work provides a new idea for research of MnO catalysts for ORR in the future.     

Microstructure and hydrogen storage properties of Ti–V–Cr based BCC-type high entropy alloys

In this work, the crystal structure and hydrogen storage properties of V₃₅Ti₃₀Cr₂₅Fe₁₀, V₃₅Ti₃₀Cr₂₅Mn₁₀, V₃₀Ti₃₀Cr₂₅Fe₁₀Nb₅ and V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ BCC-type high entropy alloys have been investigated. It was found that high entropy promotes the formation of BCC phase while large atomic difference (δ) has the opposite effect. Among the four alloys, the V₃₅Ti₃₀Cr₂₅Mn₁₀ alloy shows the highest hydrogen absorption capacity while the V₃₅Ti₃₀Cr₂₆Fe₅Mn₅ alloy exhibits the highest reversible capacity. The cause of the loss of desorption capacity is mainly due to the high stability of the hydrides. The higher room-temperature desorption capacity of the V₃₅Ti₃₀Cr₂₅Fe₅Mn₅ alloy is due to higher hydrogen desorption pressure. After pumping at 400 °C, the hydrides can return to the original BCC structure with only a small expansion in the cell volume.     

Multiscale insights into hydrogen charging behavior in metal hydride reactor packed with porous ZrCo particles

The primary purpose of this work is to develop a novel model for comprehensively investigating the hydrogen storage performance under the framework of diffusion of hydrogen atoms through hydride layer. The proposed model is constructed upon perfectly mathematical-physical equations, by taking into account complicated multi-scale and multi-physics coupling actions. Importantly, three-dimensional numerical simulations are performed to explore the coupling effects of micro diffusion, mesoscopic permeation, and macroscopic fluid flow. An analytical approach accounting for the characteristics of reaction bed, particle, and crystal grain is presented as well. In addition, a parametric analysis is conducted to reveal that the hydride particle dimension, particle porosity, grain size, and diffusion coefficient of reacted layer have a significant effect on overall hydrogen storage performance, highlighting that grain size and hydrogen diffusion coefficient are vital factors that need to be considered for material preparation and design.     

Cu-assisted induced atomic-level bivalent Fe confined on N-doped carbon concave dodecahedrons for acid oxygen reduction electrocatalysis

Atomically dispersed transition metals anchored on N-doped carbon have been successfully developed as promising electrocatalysts for acidic oxygen reduction reaction (ORR). Nonetheless, how to introduce and construct single-atomic active sites is still a big challenge. Herein, a novel concave dodecahedron catalyst of N-doped carbon (FeCuNC) with well confined atomically dispersed bivalent Fe sites was facilely developed via a Cu-assisted induced strategy. The obtained catalyst delivered outstanding ORR performance in 0.5 M H₂SO₄ media with a half-wave potential (E_1/2) of 0.82 V (vs reversible hydrogen electrode, RHE), stemming from the highly active bivalent Fe-N_x sites with sufficient exposure and accessibility guaranteed by the high specific surface area and curved surface. This work provides a simple but efficient metal-assisted induced strategy to tune the configurations of atomically dispersed active sites as well as microscopy structures of carbon matrix to develop promising PGM-free catalysts for proton exchange membrane fuel cell (PEMFC) applications.     

Highly efficient electrochemical generation of H2O2 on N/O co-modified defective carbon

The electrochemical oxygen reduction reaction (ORR) via two-electron pathway is a sustainable way of producing hydrogen peroxide. Nanostructured carbon materials are proved to be effective catalysts for 2e^? ORR. Herein, a series of mesoporous carbon with tunable nitrogen species and oxygen functional groups were synthesized by varying the added amount of dopamine hydrochloride as nitrogen and oxygen source. The modified catalysts exhibited higher content of pyrrolic-N and ether C–O groups which are confirmed by a series of characterization. Raman spectra and correlation analysis revealed that the increased proportion of defect sites in carbon materials are closely related to the introduced pyrrolic-N and ether C–O groups. And the rotating ring-disk electrode (RRDE) measurement carried out in 0.1 M KOH electrolyte showed the H₂O₂ selectivity increased with the content of defect sites. Among them, the optimized catalyst (NOC-6M) exhibited a selectivity of 95.2% and a potential of 0.71 V vs. RHE at ?1 mA cm^?2. Moreover, NOC-6M possessed the high H₂O₂ production rate of 548.8 mmol g_cat^?1 h^?1 with faradaic efficiency of 92.4% in a two-chamber H-cell. Further mechanistic analysis revealed that the introduction of pyrrolic-N and ether C–O are likely to improve the binding energy of the defect sites toward 1OOH intermediate, resulting in a more favorable 2e^? ORR pathway for H₂O₂ production.     

Rate equation theory for the hydrogenation kinetics of Mg-based materials

A uniform solid product layer normally assumed in the shrinking-core model cannot predict the kinetic transition behavior of the H₂ adsorption reactions. In this study, the concept of a uniform solid product layer has been replaced by that of the inward growth of solid products on the solid surface. A rate equation is established to calculate the inward growth of the solid product and was implemented into the shrinking-core model to calculate the H₂ adsorption kinetics for various shapes of Mg-based materials. The prediction accuracy of the developed model is verified from the detailed experimental data. To account for the external gas diffusion around the particle and the intraparticle gas diffusion, an analytical equation is derived using the Thiele modulus method. This model can be used to analyze various kinetic aspects and to analyze the effect of change in the particle microstructure on intraparticle diffusion.     

Top-down preparation of Ni–Pd–P@graphitic carbon core-shell nanostructure as a non-Pt catalyst for enhanced electrocatalytic reactions

Electrochemical reactions such as the oxygen evolution reaction (OER), oxygen reduction reaction (ORR), and methanol oxidation reaction (MOR) are essential for energy conversion applications such as water electrolysis and fuel cells. Furthermore, Pt or Ir-related materials have been extensively utilized as electrocatalysts for the OER, ORR, and MOR. To reduce the utilization of precious metals, innovative catalyst structures should be proposed. Herein, we report a bi-metallic phosphide (Ni₂P and PdP₂) structure surrounded by graphitic carbon (Ni–Pd–P/C) with an enhanced electrochemical activity as compared to conventional electrocatalysts. Despite the low Pd content of 3 at%, Ni–Pd–P/C exhibits a low overpotential of 330 mV at 10 mA cm^?2 in the OER, high specific activity (2.82 mA cm^?2 at 0.8 V) for the ORR, and a high current density of 1.101 A mg^?1 for the MOR. The superior electrochemical performance of Ni–Pd–P/C may be attributed to the synergistic effect of the bi-metallic phosphide structure and core-shell structure formed by graphitic carbon.     

Hydrogen generation rate enhancement by in situ Fe(0) and nitroarene substrates in Fe3O4@Pd catalyzed ammonia borane hydrolysis and nitroarene reduction tandem reaction

We report the catalytic enhancement of hydrogen generation by 1) in situ Fe (0) formed and 2) nitroarenes substrates during Fe₃O₄@Pd core-shell nanoparticles catalyzed tandem reaction. The active hydrogen species are generated in Pd shell, which either combine to form H₂ gas or take part in relatively faster nitroarene reduction reaction. The rate of hydrogen generation from ammonia borane is dependent on the nitroarene substrate and is higher when 4-nitrophenol is used. This is due to the difference in ammonia borane adsorption on the surface of the catalyst. During recyclability, the H₂ generation rate of 2 wt% Pd loaded samples is higher than other compositions. Such an enhancement has been attributed to the formation of Fe (0) via γ-FeOOH mediated by Pd species, presumably through Pd(OH)₂. The electronic connection between Fe and Pd interface is thus shown to play an important role in the catalytic enhancement of the tandem reaction.