Recent progress of electrocatalysts for hydrogen proton exchange membrane fuel cells

Due to stringent environmental regulations and the limited resources of fossil-based fuels, there is an urgent demand for clean and eco-friendly energy conversion devices. These criteria appear to be met by hydrogen proton exchange membrane fuel cells (PEMFCs). PEMFCs have attracted tremendous attention on account of their excellent performance with tunable operability and good portability. Nonetheless, their practical applications are hugely influenced by the scarcity and high cost of platinum (Pt) used as electrocatalysts at both cathode and anode. Pt is also susceptible to easy catalyst poisoning. Herein, this paper reviews the progress of the research regarding the development of electrocatalysts practically used in hydrogen PEMFCs, where the corner-stone reactions are cathodic oxygen reduction reaction (ORR) and anodic hydrogen oxidation reaction (HOR). To reduce the costs of PEMFCs, lessening or eliminating the use of Pt is of prime importance. For current and forthcoming laboratory/large-scale PEMFCs, there is much interest in developing substitute catalysts based on cheaper materials. As such are non-platinum (non-Pt), non-platinum group metals (non-PGMs), metal oxides, and non-metal electrocatalysts. Hence, high-performance, state-of-the-art, and novel structured electrocatalysts as replacements for Pt are needed.     

Catalytic combustion synthesis of CNTs/MgO composite powders and the influences on the thermal shock resistance of low-carbon Al2O3–C refractories

Using MgC₂O₄, Mg powders as raw materials and Ni(NO₃)₂?6H₂O as a catalyst, CNTs/MgO composite powders were prepared by a catalytic combustion synthesis method. The CNTs/MgO composite powders were characterized by XRD, Raman spectroscopy, FESEM/EDS and HRTEM. The effects of catalyst content on the degree of graphitization and aspect ratio of the CNTs in composite powders were investigated. Moreover, the thermal shock resistance of low-carbon Al₂O₃–C refractories after adding the composite powder was investigated. The results indicated that the CNTs prepared with 1 wt% Ni(NO₃)₂?6H₂O addition had a higher degree of graphitization and aspect ratio. In particular, the aspect ratio could reach approximately 200. The growth mechanism of hollow bamboo-like CNTs in the composite powders was proven to be a V-L-S mechanism. The thermal shock resistance of Al₂O₃–C samples could be improved significantly after adding CNTs/MgO composite powders. In particular, compared with CM0, the residual strength ratio of Al₂O₃–C samples with added 2.5 wt% composite powders could be increased 63.9%.     

Increased hydroxyl concentration by tungsten oxide modified h-BN promoted catalytic performance in partial oxidation of methane

Hexagonal boron nitride (h-BN) as a layered inorganic nonmetallic material has been widely used. Hydrogen peroxide (H₂O₂) modification can trigger exfoliation and afford abundant B–OH active sites at edge of h-BN, which can enhance methane activation ability. Introducing tungsten oxide (WO₃) to h-BN produces a similar effect, because doping WO₃ into h-BN resulted in electron transfer to N, inducing fracture of B–N bond, resulting in N vacancy (triboron center), exposing more B sites and promoting the generation of B–OH. Significantly, the introduction of WO₃ on the modified h-BN dramatically increased the concentration of B–OH compared with the unmodified h-BN, because H₂O₂ modification weakened B–N bond. By means of XRD, TEM, XPS,EPR, FT-IR, it is proved that the high concentration of B–OH active sites contributed to activating C–H bond, thus methane conversion and CO and H₂ selectivity were significantly improved.     

Achieving superior hydrogen storage properties via in-situ formed nanostructures: A high-capacity Mg–Ni alloy with La microalloying

Mg-based hydride is a promising hydrogen storage material, but its capacity is hindered by the kinetic properties. In this study, Mg–Mg₂Ni–LaH_x nanocomposite is formed from the H-induced decomposition of Mg₉₈Ni_1·67La_0.33 alloy. The hydrogen capacity of 7.19 wt % is reached at 325 °C under 3 MPa H₂, attributed to the ultrahigh hydrogenation capacity in Stage I. The hydrogen capacity of 5.59 wt % is achieved at 175 °C under 1 MPa H₂. The apparent activation energies for hydrogen absorption and desorption are calculated as 57.99 and 107.26 kJ/mol, which are owing to the modified microstructure with LaH_x and Mg₂Ni nanophases embedding in eutectic, and tubular nanostructure adjacent to eutectic. The LaH_2.49 nanophase can catalyze H₂ molecules to dissociate and H atoms to permeate due to its stronger affinity with H atoms. The interfaces of these nanophases provide preferential nucleation sites and alleviate the “blocking effect” together with tubular nanostructure by providing H atoms diffusion paths after the impingement of MgH₂ colonies. Therefore, the superior hydrogenation properties are achieved because of the rapid absorption process of Stage I. The efficient synthesis of nano-catalysts and corresponding mechanisms for improving hydrogen storage properties have important reference to related researches.     

A dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanopaticles showing significant electrocatalytic activity towards ethanol oxidation reaction (EOR)

To the best of our knowledge, this is the first time to report the preparation of a dotted nanowire arrayed by 5 nm sized palladium and nickel composite nanoparticles (denoted as Pd_xNi_y NPs) via a hydrothermal method using NU and PdO·H₂O as the starting materials. The samples prepared at the mass ratio of NU to PdO·H₂O 1:1, 1:2 and 2:1 were, respectively, nominated as catalyst c₁, c₂ and c₃. The chemical compositions of all synthesized catalysts were mainly studied by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), revealing that metallic Ni was one main component of all prepared catalysts. Surprisingly, the main diffraction peaks appearing in the XRD patterns of all prepared catalysts were assigned to the metallic Ni rather than the metallic Pd. Very interestingly, as indicated by the TEM images, a large number of dotted nanowires arrayed by numerous equidistant 5 nm sized nanoparticles were distinctly exhibited in catalyst c₁. More importantly, when being used as electrocatalysts for EOR, all prepared catalysts exhibited an evident electrocatalytic activity towards EOR. In the cyclic voltammetry (CV) test, the peak current density of the forward peak of EOR on catalyst c₁ measured at 50 mV s^?1 was as high as 56.1 mA cm^?2, being almost 9 times higher than that of EOR on catalyst c₃ (6.3 mA cm^?2). Particularly, the polarized current density of EOR on catalyst c₁ at 3600 s, as indicated by the chronoamperometry (CA) experiment, was still maintained to be around 1.47 mA cm^?2, a value higher than the latest reported data of 1.3 mA cm^?2 (measured on the pure Pd/C electrode). Presenting a novel method to prepare dotted nanowires arranged by 5 nm sized nanoparticles and showing the significant eletrocatalytic activities of the newly prepared dotted nanowires towards EOR were the major contributions of this preliminary work.     

High-temperature oxidation behavior of monolithic Zr3[Al(Si)]4C6 and its composite incorporating 30vol% ZrB2-SiC: Providing a basis for broadening the service temperature

To provide a basis for the high-temperature oxidation of ultra-high temperature ceramics (UHTCs), the oxidation behavior of Zr₃[Al(Si)]₄C₆ and a novel Zr₃[Al(Si)]₄C₆-ZrB₂-SiC composite at 1500 °C were investigated for the first time. From the calculation results, the oxidation kinetics of the two specimens follow the oxidation dynamic parabolic law. Zr₃[Al(Si)]₄C₆ exhibited a thinner oxide scale and lower oxidation rate than those of the composite under the same conditions. The oxide scale of Zr₃[Al(Si)]₄C₆ exhibited a two-layer structure, while that of the composite exhibited a three-layer structure. Owing to the volatilization of B₂O₃ and the active oxidation of SiC, a porous oxide layer formed in the oxide scale of the composite, resulting in the degradation of its oxidation performance. Furthermore, the cracks and defects in the oxide scale of the composite indicate that the reliability of the oxide scale was poor. The results support the service temperature of the obtained ceramics.     

Unipolar plasma electrolytic oxidation: Waveform optimisation for corrosion resistance of commercially pure titanium

This study deals with the anodisation of titanium grade 2 in 0.5-M sulphuric acid using a pulsed signal in a unipolar regime. The electrical parameters investigated are voltage, frequency and duty cycle. The use of duty cycles with a high percentage of anodic polarisation (90%), combined with high frequencies (1000 Hz) and the higher voltage tested (220 V), favoured the establishment of a plasma regime involving strong dielectric discharges, allowing the growth of thicker oxides but with rough architecture. The corrosion resistance of the formed film has been characterised by potentiodynamic tests in 0.5-M NaBr for localised corrosion resistance and by immersion tests in 10% v/v sulphuric acid solution for a uniform corrosion assessment. Current–time curves, visual observations and electron microscope analysis (scanning electron microscopy, energy-dispersive X-ray spectroscopy) were the tools selected to provide a correlation between technological parameters and oxide growth mechanism. For localised and uniform corrosion, anodisation at 220 V with a high level of anodic polarisation (90%) and frequency (1000 Hz) was verified to be particularly advantageous.     

An infinite chain, {[Ni(tn)2]3[Fe(CN)4(μ-CN)2]2}n,a new catalyst for electrochemical-driven water splitting and photochemical-driven hydrogen evolution from water under blue light

A new catalyst for both water reduction and oxidation, based on an infinite chain, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n, is formed by the reaction of NiCl₂, 1,3-propanediamine (tn) and K₃ [Fe(CN)₆]. {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can electro-catalyze hydrogen evolution from a neutral aqueous buffer (pH 7.0) with a turnover frequency (TOF) of 1561 mol of hydrogen per mole of catalyst per hour (H₂/mol catalyst/h) at an overpotential (OP) of 837 mV {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n also can electro-catalyze O₂ production from water with a TOF of ～45 mol O₂ (mol cat)^?1s^?1 at an OP of 591 mV. Under blue light (λ = 469 nm), together with CdS nanorods (CdS NRs) as a photosensitizer, and ascorbic acid (H₂A) as a sacrificial electron donor, {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n can photo-catalyze hydrogen generation from an aqueous buffer (pH 4.0) with a turnover number (TON) of 11,450 mol H₂ per mole of catalyst (mol of H₂ (mol of cat)^?1) during 10 h irradiation. The average of apparent quantum yield (AQY) is as high as 40.96% during 10 h irradiation. Studies indicate that {[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n exists in two forms: a cyano-bridged chain ({[Ni(tn)₂]₃ [Fe(CN)₄ (μ-CN)₂]₂}_n) in solid, and a salt ([Ni(tn)₂]₃ [Fe(CN)₆]₂) in aqueous media; Catalytic reaction occurs on the nickel center of [Ni(tn)₂]²⁺, and the introduction of [Fe(CN)₆]^3- can improve the catalytic efficiency of [Ni(tn)₂]²⁺ for H₂ or O₂ generation. We hope these findings can afford a new method for the design of catalysts for both water reduction and oxidation.     

Preparation of Pt/Ce–Zr–Y mixed oxide/anodized aluminium oxide catalysts for hydrogen passive autocatalytic recombination

The use of a Pt-based catalyst was evaluated for autocatalytic hydrogen recombination. The Pt was supported on a mixture of Ce-, Zr- and Y-oxides (CZY) to yield nanosized Pt particles. The Pt/CZY/AAO catalyst was then prepared by the spray-deposition of the Pt/CZY intermediate onto an anodized aluminium oxide (AAO) layer on a metallic aluminum core. The Pt/CZY/AAO catalyst (3 × 1 cm) was evaluated for hydrogen combustion (1–8 vol% hydrogen in the air) in a recombiner section testing station. The thermal distribution throughout the catalyst surface was investigated using an infrared camera. The maximum temperature gradient (ΔT) for the examined hydrogen concentrations did not exceed 36 °C. The Pt/CZY/AAO catalyst was also evaluated for prolonged hydrogen combustion duration to assess its durability. An average combustion temperature of 239.0 ± 10.0 °C was maintained for 53 days of catalytic hydrogen combustion, suggesting that there was limited, or no, catalyst deactivation. Finally, a Pt/CZY/AAO catalytic plate (14.0 × 4.5 cm) was prepared to investigate the thermal distribution. An average surface temperature of 212.5 °C and a maximum ΔT of 5.4 °C was obtained throughout the catalyst surface at a 3 vol% hydrogen concentration.     

Highly stable nanocarbon supported Pt catalyst for fuel cell via a molten salt graphitization strategy

Proton exchange membrane fuel cells (PEMFCs) durability has been severely hindered by carbon support poor stability in the cathodic Pt-based catalyst. Herein, a high-surface-area nitrogen-doped graphitic nanocarbon (N-G-CA) with mesopores is developed as Pt support to address PEMFCs durability challenge. Resorcinol-formaldehyde aerogel pyrolyzed carbon aerogel is selected as N-G-CA raw material. Nitrogen atoms are introduced into carbon aerogel via NH₃ heat treatment. Then, nitrogen-doped carbon aerogel is transferred into N-G-CA via heating together with transition-metal salts (one of FeCl₃, FeCl₂, CoCl₂, or MnCl₂, etc.) at 1200 °C. As ORR catalyst, Pt/N-G-CA half-wave potential only lost 10 mV, after 30, 000 cycles accelerated aging test in the rotating-desk-electrode. Only 12 mV voltage loss at 1.5 A/cm2 is observed, after 5, 000 cycles for membrane electrode. Pt/N-G-CA exhibits superior durability and activity than commercial Pt/C. High durability of Pt/N-G-CA is due to N-G-CA high graphitization extent, as well as the interactions between doping nitrogen and Pt. N-G-CA is promising as stable support for durable Pt-based catalysts in PEMFCs, thanks to enhanced carbon corrosion resistance, uniformly dispersed Pt, and strong support-metals interaction.