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.     

Numerical approach to analyze fluid flow in a type C tank for liquefied hydrogen carrier (part 1: Sloshing flow)

The demand for clean energy use has been increasing worldwide, and hydrogen has attracted attention as an alternative energy source. The efficient transport of hydrogen must be established such that hydrogen may be used as an energy source. In this study, we considered the influences of various parameters in the transportation of liquefied hydrogen using type C tanks in shipping vessels. The sloshing and thermal flows were considered in the transportation of liquefied hydrogen, which exists as a cryogenic liquid at ?253 °C. In this study, the sloshing flow was analyzed using a numerical approach. A multiphase sloshing simulation was performed using the volume of fluid method for the observation and analysis of the internal flow. First, a sloshing experiment according to the gas-liquid density ratio performed by other researchers was utilized to verify the simulation technique and investigate the characteristics of liquefied hydrogen. Based on the results of this experiment, a sloshing simulation was then performed for a type C cargo tank for liquefied hydrogen carriers under three different filling level conditions. The sloshing impact pressure inside of the tank was measured via simulation and subjected to statistical analysis. In addition, the influence of sloshing flow on the appendages installed inside of the type C tank (stiffened ring and swash bulkhead) was quantitatively evaluated. In particular, the influence of the sloshing flow inside of the type C tank on the appendages can be utilized as an important indicator at the design stage. Furthermore, if such sloshing impact forces are repeatedly experienced over an extended period of time under cryogenic conditions, the behavior of the tank and appendages must be analyzed in terms of fatigue and brittle failure to ensure the safety of the transportation operation.     

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.     

基于误差估值累加开环校正的诱导式欺骗检测方法

诱导式卫星欺骗干扰可诱导航空器逐渐偏离预定航迹，难以被发现，因此及时有效地检测干扰是飞行安全的保障。在现有紧组合导航体制基础上，设计了一种基于误差估值累加开环校正的紧组合导航结构，并证明了其性能与传统闭环校正紧组合导航性能等效。在此结构中，将紧组合导航系统与自适应序贯概率比检测方法结合，提出了一种基于误差估值累加开环校正的诱导式欺骗检测方法，融合紧组合导航信息与其他不受欺骗影响的导航信息，构建欺骗检测统计量进行诱导式欺骗检测。仿真结果表明，开环校正结构可避免随时间累加的惯性导航系统误差所导致的组合导航滤波器发散问题，同时欺骗检测方法可进一步提高算法对“最坏”情形下微小诱导式欺骗的检测效果。     

基于滚动摩擦作用下玉米颗粒在模拟筒仓卸料中的力链分析（网络首发、推荐阅读）

针对颗粒滚动摩擦作用对筒仓中玉米颗粒的力链空间分布进行研究，通过EDEM离散元软件建立筒仓模型与仿真玉米颗粒模型进行卸粮仿真模拟，并与筒仓卸料实验作流态对比，验证模型与仿真结果的准确性。通过对模拟仓进行切片观察和数据处理，对比分析了不同摩擦情况下力链的细观参数随时间演化规律。模拟结果表明：颗粒间摩擦系数越大，卸粮完成的最终时间越长；颗粒间滚动摩擦系数越小，颗粒由整体流转变为管状流的时间越早。对于有漏斗的筒仓来说，减小颗粒间摩擦会改变整体流和管状流之间的极限，从而增加产生管状流的面积。标准滚动摩擦系数下玉米颗粒在卸料过程中会出现起拱-塌陷效应；减小滚动摩擦，玉米颗粒卸料较稳定，未出现起拱的应力突增、以及拱塌陷的应力衰减；增大颗粒间滚动摩擦不但会增加拱效应，且出现成拱高度距离漏斗口更高。     

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 adaptive sliding mode observer based near-optimal OER tracking control approach for PEMFC under dynamic operation condition

Tracking control of oxygen excess ratio (OER) is crucial for dynamic performance and operating efficiency of the proton exchange membrane fuel cell (PEMFC). OER tracking errors and overshoots under dynamic load limit the PEMFC output power performance, and also could lead oxygen starvation which seriously affect the life of PEMFC. To solve this problem, an adaptive sliding mode observer based near-optimal OER tracking control approach is proposed in this paper. According to real time load demand, a dynamic OER optimization strategy is designed to obtain an optimal OER. A nonlinear system model based near-optimal controller is designed to minimize the OER tracking error under variable operation condition of PEMFC. An adaptive sliding mode observer is utilized to estimate the uncertain parameters of the PEMFC air supply system and update parameters in near-optimal controller. The proposed control approach is implemented in OER tracking experiments based on air supply system of a 5 kW PEMFC test platform. The experiment results are analyzed and demonstrate the efficacy of the proposed control approach under load changes, external disturbances and parameter uncertainties of PEFMC system.     

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.