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.     

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.     

基于跨临界CO2热泵的茶叶生产能源系统负荷削减潜力

乡村产业中的化石能源设备逐渐被电能技术替代，引起了乡村负荷波动增大、部分时段产生集中高负荷的问题。为了解决以上问题，将低品位清洁能源应用至乡村的茶叶生产中，针对烘茶全过程的工艺要求提出了跨临界CO₂热泵烘茶技术；并以某茶叶生产乡村为对象，对其代表台区的全年日用电量及产茶日负荷进行了分析，得出采用CO₂热泵烘茶后其负荷得到大幅度削减，整体可降低至原负荷的39.6%~46.8%，峰值负荷与平时负荷的比值由原本的13.6降至5.4~6.2。跨临界CO₂热泵应用至农产品生产中可有效缓解乡村供电压力。     

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.     

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.     

An integrated dimensionality reduction and surrogate optimization approach for plant-wide chemical process operation

With liquefied natural gas becoming increasingly prevalent as a flexible source of energy, the design and optimization of industrial refrigeration cycles becomes even more important. In this article, we propose an integrated surrogate modeling and optimization framework to model and optimize the complex CryoMan Cascade refrigeration cycle. Dimensionality reduction techniques are used to reduce the large number of process decision variables which are subsequently supplied to an array of Gaussian processes, modeling both the process objective as well as feasibility constraints. Through iterative resampling of the rigorous model, this data-driven surrogate is continually refined and subsequently optimized. This approach was not only able to improve on the results of directly optimizing the process flow sheet but also located the set of optimal operating conditions in only 2 h as opposed to the original 3 weeks, facilitating its use in the operational optimization and enhanced process design of large-scale industrial chemical systems.     

Boron doping induced electronic reconfiguration of Fe-Nx sites in N-doped carbon matrix for efficient oxygen reduction reaction in both alkaline and acidic media

Developing non-precious metal-based catalysts as the substitution of precious catalysts (Pt/C) in oxygen reduction reaction (ORR) is crucial for energy devices. Herein, a template and organic solvent-free method was adopted to synthesize Fe, B, and N doped nanoflake-like carbon materials (Fe/B/N–C) by pyrolysis of monoclinic ZIF-8 coated with iron precursors and boric acid. Benefiting from introducing B into Fe–N–C, the regulated electron cloud density of Fe-N_x sites enhance the charge transfer and promotes the ORR process. The as-synthesized Fe/B/N–C electrocatalyst shows excellent ORR activity of a half-wave potential (0.90 V vs 0.87 V of Pt/C), together with superior long-term stability (95.5% current density retention after 27 h) in alkaline media and is even comparable to the commercial Pt/C catalyst (with a half-wave potential of 0.74 V vs 0.82 V of Pt/C) in an acidic electrolyte. A Zn-air battery assembled with Fe/B/N–C as ORR catalyst delivers a higher open-circuit potential (1.47 V), specific capacity (759.9 mA h g^?1_Zn at 10 mA cm^?2), peak power density (62 mW cm^?2), as well as excellent durability (5 mA cm^?2 for more than 160 h) compared to those with commercial Pt/C. This work provides an effective strategy to construct B doped Fe–N–C materials as nonprecious ORR catalyst. Theoretical calculations indicate that introduction of B could induce Fe-N_x species electronic configuration and is favorable for activation of OH1 intermediates to promote ORR process.