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.     

Fe(III) grafted MoO3 nanorods for effective electrocatalytic fixation of atmospheric N2 to NH3

Electrocatalytic nitrogen reduction reaction (ENRR) offers a carbon-neutral process to fix nitrogen into ammonia, but its feasibility depends on the development of highly efficient electrocatalysts. Herein, we report that Fe ion grafted on MoO₃ nanorods synthesized by an impregnation technique can efficiently enhance the electron harvesting ability and the selectivity of H⁺ during the NRR process in neutral electrolyte. In 0.1 M Na₂SO₄ solution, the electrocatalyst exhibited a remarkable NRR activity with an NH₃ yield of 9.66 μg h^?1 mg^?1_cat and a Faradaic efficiency (FE) of 13.1%, far outperforming the ungrafted MnO₃. Density functional theory calculations revealed that the Fe sites are major activation centers along the alternating pathway.     

Enhanced electrocatalytic oxygen reduction reaction from organic-inorganic heterostructure

Herein, molybdenum disulfide nanoflakes decorated copper phthalocyanine microrods (CuPc-MoS₂) are synthesized via two step simple hydrothermal method. The as synthesized hybrid along with pure molybdenum disulfide (MoS₂) nanoflower and pure copper phthalocyanine (CuPc) microrods are well characterized by various techniques that confirm phase, morphology, elemental compositions etc. Next, electrocatalytic oxygen reduction reaction towards fuel cell is investigated in alkaline medium and obtained results proclaim that our CuPc-MoS₂ heterostructure outperforms the other two constituent materials. Efficient oxygen reduction is achieved following four electron pathway by CuPc-MoS₂ whereas partial reduction is done through two electron process by CuPc and MoS₂ separately. Long-time durability test reveals almost 97.6% retention after 8000s that eventually dictate us that CuPc-MoS₂ heterostructure can be the efficient cathode electrocatalyst for future generation fuel cell.     

Effect of mesoporous carbon on oxygen reduction reaction activity as cathode catalyst support for proton exchange membrane fuel cell

In this paper, a new carbon support with a large number of mesoporous-structures is selected to prepare Pt/C catalysts. Transmission electron microscope (TEM) results show that the Pt/3# catalyst presents a sponge-like morphology, Pt particles are not only evenly distributed on the surface of carbon support, but also the smaller Pt particles are deposited in the mesoporous inside the support. The average diameter of Pt particles is only 2.8 nm. The membrane electrode assembly (MEA) based on Pt/3# catalyst also shows excellent performance. In conclusion, the 3# support is an idea carbon support for PEMFC, which helps to improve the oxygen reduction reaction (ORR) activity of the catalyst. Based on the “internal-Pt” structure of the support mesoporous, the efficient three-phase boundaries (TPBs) are construct to avoid the poisoning effect of ionomer on the nano-metal particles, reduce the activation impedance and oxygen mass transfer impedance, and improve the reaction efficiency.     

Numerical simulation of water and heat transport in the cathode channel of a PEM fuel cell

Cathode channel of a PEM fuel cell is the critical domain for the transport of water and heat. In this study, a mathematical model of water and heat transport in the cathode channel is established by considering two-phase flow of water and air as well as the phase change between water and vapor. The transport process of the species of air is governed by the convection-diffusion equation. The VOSET (coupled volume-of-fluid and level set method) method is used to track the interface between air and water, and the phase equilibrium method of water and vapor is employed to calculate the mass transfer rate on the two-phase interface. The present model is validated against the results in the literature, then applied to investigate the characteristics of two-phase flow and heat transfer in the cathode channel. The results indicate that in the inlet section, water droplets experience three evolution stages: the growing stage, the coalescence stage and the generation stage of dispersed water drops. However, in the middle and outlet sections of the channel, there are only two stages: the growth of water droplets, and the formation of a water film. The mass transfer rate of phase change in the inlet section of the channel varies over time, exhibiting an initial increase, a decrease followed, and a stabilization finally, with the maximum and stable values of 1.78 × 10^?4 kg/s and 1.52 × 10^?4 kg/s for Part 1, respectively. In the middle and outlet sections, the mass transfer rate increase firstly and then keeps stable gradually. Furthermore, regarding the distribution of the temperature and vapor mass fraction in the channel, near the upper surface of the channel, the temperature and vapor mass fraction first change slightly (x < 0.03 m) and then rapidly decrease with fluctuations (x > 0.03 m). In the middle of the channel, the temperature and vapor mass fraction slowly decrease with fluctuation.     

Synthesis and performance evaluation of a new drag reducer based on acrylamide/12-allyloxydodecyl acid sodium

Hydraulic fracturing with slickwater is a field-proven stimulation technology used in tight reservoirs. Because of the high pumping rate associated with slickwater fracturing, drag reduction (DR) is critical in minimizing pressure drop and the success of oilfield operations. In this paper, a new type of drag reducer (SPR) was synthesized with acrylamide and 12-allyloxydodecyl acid sodium, and its drag reduction performance was evaluated. The results showed that the new drag reducer features low molecular weight, fast-dissolving rate and low interfacial tension. The algorithm of estimating the drag reduction rate of non-Newtonian fluid SPR was proposed and validated. Empirical or semianalytical models for estimating the friction ratio (σ) or friction factor (λ or f) were used to simulate the turbulence behavior of the SPR drag reducer under different Reynolds numbers (Re). The modified Virk's correlation could accurately model the turbulent behavior of the SPR drag reducer. A unified calculation formula was established in this study for different pipe diameters.     

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.     

Effects of upholstery materials on the burning behavior of real‐scale residential upholstered furniture mock‐ups

Fire spread and growth on real‐scale four cushion mock‐ups of residential upholstered furniture (RUF) were investigated with the goal of identifying whether changes in five classes of materials (barrier, flexible polyurethane foam, polyester fiber wrap, upholstery fabric, and sewing thread), referred to as factors, resulted in statistically significant changes in burning behavior. A fractional factorial experimental design plus practical considerations yielded a test matrix with 20 material combinations. Experiments were repeated a minimum of two times. Measurements included fire spread rates derived from video recordings and heat release rates (HRRs). A total of 13 experimental parameters (3 based on the videos and 10 on the HRR results), referred to as responses, characterized the measurements. Statistical analyses based on Main Effects Plots (main effects) and Block Plots (main effects and factor interactions) were used. The results showed that three of the factors resulted in statistically significant effects on varying numbers of the 13 responses. The Barrier and Fabric factors had the strongest main effects with roughly comparable magnitudes. Foam was statistically significant for fewer of the responses and its overall strength was weaker than for Barrier and Fabric. No statistically significant main effects were identified for Wrap or Thread. Multiple two‐term interactions between factors were identified as being statistically significant. The Barrier*Fabric interaction resulted in the highest number of and strongest statistically significant effects. The existence of two‐term interactions means that it will be necessary to consider their effects in approaches designed to predict the burning behavior of RUF.     

Hall current effects on MHD flow of chemically reacting fluid through a porous medium with heat source

We considered the magnetohydrodynamic (MHD) free convective flow of an incompressible electrically conducting viscous fluid past an infinite vertical permeable porous plate with a uniform transverse magnetic field, heat source and chemical reaction in a rotating frame taking Hall current effects into account. The momentum equations for the fluid flow during absorbent medium are controlled by the Brinkman model. Through the undisturbed state, both the plate and fluid are in a rigid body rotation by the uniform angular velocity perpendicular to an infinite vertical plate. The perpendicular surface is subject to the homogeneous invariable suction at a right angle to it and the heat on the surface varies about a non-zero unvarying average whereas the warmth of complimentary flow is invariable. The systematic solutions of the velocity, temperature, and concentration distributions are acquired systematically by utilizing the perturbation method. The velocity expressions consist of steady-state and fluctuating situations. It is revealed that the steady part of the velocity field has a three-layer characteristic while the oscillatory part of the fluid field exhibits a multi-layer characteristic. The influence of various governing flow parameters on the velocity, temperature, and concentration are analyzed graphically. We also discuss computational results for the skin friction, Nusselt number, and Sherwood number in the tabular forms.     

NiFe layered double hydroxide as an efficient bifunctional catalyst for electrosynthesis of hydrogen peroxide and oxygen

Two electron oxygen reduction reaction to produce hydrogen peroxide (H₂O₂) is a promising alternative technique to the multistep and high energy consumption anthraquinone process. Herein, Ni–Fe layered double hydroxide (NiFe-LDH) has been firstly demonstrated as an efficient bifunctional catalyst to prepare H₂O₂ by electrochemical oxygen reduction (2e^? ORR) and oxygen evolution reaction (OER). Significantly, the NiFe-LDH catalyst possesses a high faraday efficiency of 88.75% for H₂O₂ preparation in alkaline media. Moreover, the NiFe-LDH catalyst exhibits excellent OER electrocatalytic property with small overpotential of 210 mV at 10 mA cm^?2 and high stability in 1 M KOH solution. On this basis, a new reactor has been designed to electrolyze oxygen and generate hydrogen peroxide. Under the ultra-low cell voltage of 1 V, the H₂O₂ yield reaches to 47.62 mmol g_cat^?1 h^?1. In order to evaluate the application potential of the bifunctional NiFe-LDH catalyst for H₂O₂ preparation, a 1.5 V dry battery has been used as the power supply, and the output of H₂O₂ reaches to 83.90 mmol g_cat^?1 h^?1. The excellent electrocatalytic properties of 2e^? ORR and OER make NiFe-LDH a promising bifunctional electrocatalyst for future commercialization. Moreover, the well-designed 2e^? ORR-OER reactor provides a new strategy for portable production of H₂O₂.