Non-Platinum Group Metal Electrocatalysts toward Efficient Hydrogen Oxidation Reaction

Developing non-platinum group metal (non-PGM) electrocatalysts for the hydrogen oxidation reaction (HOR) represents the efforts towards the more economical use of hydrogen fuel cells and hydrogen energy, which has attracted tremendous attention recently. However, non-PGM electrocatalysts for the HOR are still in their early development stages as compared with the significant advances in those for the oxygen reduction reaction and hydrogen evolution reaction. Herein, this paper summarizes the recent progresses and highlights the key challenges for the rational design of non-PGM electrocatalysts, aiming to promote the development of non-PGM HOR electrocatalysts. Fundamental understandings of the HOR mechanism are firstly reviewed, where theoretical interpretations on the low HOR kinetics in alkaline media, including the hydrogen binding energy theory, the bifunctional mechanism, and the water molecule reorganization, are particularly discussed. Subsequently, progresses of typical non-PGM HOR electrocatalysts in acid and alkaline media are summarized separately. For the HOR under alkaline conditions, the superiorities and challenges of Ni-based catalysts are discussed with a particular focus as they are the most promising non-PGM electrocatalysts. Finally, this paper highlights the challenges and provide perspectives on the future development directions of non-PGM HOR electrocatalysts.     

Potassium titanate whiskers on the walls of cordierite honeycomb ceramics for soot catalytic combustion

In this paper, potassium titanate whiskers was prepared via the Molten salt synthesis on the surface of cordierite ceramics for the regeneration of diesel particulate filters (DPFs). SEM, EDS, XRD, FT-IR, TG-DSC and TPO were carried out to characterize the morphology, microstructure, growth mechanism and catalytic performance of the samples. Potassium titanate whiskers with diameter (100–500 nm) and length (about 3 μm) is tightly combined with the cordierite ceramic substrate. The catalyst performance investigation demonstrates that potassium titanate whiskers decrease the soot combustion temperature apparently. The soot combustion process was studied by thermal analysis tests, and the activation energy of the combustion reaction can be calculated using Freeman-Carroll method. The carbon oxidation activation energy is 14.009 kcal/mol, and the activation energy for the catalytic reaction with potassium titanate whiskers is 6.287 kcal/mol, it can be illustrated that potassium titanate whiskers/cordierite catalyst possess excellence performance for carbon catalytic combustion. The coarseness of the interface increased because potassium titanate whiskers grew on the cordierite substrate, and the trapping ability could improve. This unique microstructure has potential application in the DPF field.     

Application of ferrous sulfate alleviates negative impact of cadmium in rice (<i>Oryza sativa</i> L.)

Soil contamination with toxic heavy metals [such as cadmium (Cd)] is becoming a serious global problem due to rapid development of social economy. Iron (Fe), being an important element, has been found effective in enhancing plant tolerance against biotic and abiotic stresses. The present study investigated the extent to which different levels of Ferrous sulphate (FeSO₄) modulated the Cd tolerance of rice (Oryza sativa L.), when maintained in artificially Cd spiked regimes. A pot experiment was conducted under controlled conditions for 146 days, by using natural soil, mixed with different levels of CdCl₂ [0 (no Cd), 0.5 and 1 mg/kg] together with the exogenous application of FeSO₄ at [0 (no Fe), 1.5 and 3 mg/kg] levels to monitor different growth, gaseous exchange characteristics, oxidative stress, antioxidative responses, minerals accumulation, organic acid exudation patterns of O. sativa. Our results depicted that addition of Cd to the soil significantly (P < 0.05) decreased plant growth and biomass, gaseous exchange parameters, mineral uptake by the plants, sugars (soluble, reducing, and non-reducing sugar) and altered the ultrastructure of chloroplasts, plastoglobuli, mitochondria, and many other cellular organelles in Cd-stressed O. sativa compared to those plants which were grown without the addition of Cd in the soil. However, Cd toxicity boosted the production of reactive oxygen species (ROS) by increasing the contents of malondialdehyde (MDA), which is the indication of oxidative stress in O. sativa and was also manifested by hydrogen peroxide (H₂O₂) contents and electrolyte leakage to the membrane bounded organelles. Although, activities of various antioxidative enzymes like superoxidase dismutase (SOD), peroxidase (POD), catalase (CAT) and ascorbate peroxidase (APX) and non-enzymatic antioxidants like phenolics, flavonoid, ascorbic acid, anthocyanin and proline contents increased up to a Cd level of 0.5 mg/kg in the soil but were significantly diminished at the highest Cd level of 1 mg/kg in the soil compared to those plants which were grown without the addition of Cd in the soil. The negative impacts of Cd injury were reduced by the application of FeSO₄ which increased plant growth and biomass, improved photosynthetic apparatus, antioxidant enzymes, minerals uptake together with diminished exudation of organic acids as well as oxidative stress indicators in roots and shoots of O. sativa by decreasing Cd retention in different plant parts. These results shed light on the effectiveness of FeSO₄ in improving the growth and upregulation of antioxidant enzyme activities of O. sativa in response to Cd stress. However, further studies at field levels are required to explore the mechanisms of FeSO₄-mediated reduction of the toxicity of not only Cd, but possibly also other heavy metals in plants.     

Regenerable Sorbents for High-Temperature Desulfurization of Syngas from Biomass Gasification

Single-metal high-temperature solid sorbents for syngas cleaning using Mn, Ca, Fe, Cu, or Mo supported on γ-Al₂O₃ were synthesized, characterized, and tested in a fixed-bed reactor. H₂S and SO₂ concentrations in the gas after treatment at T = 400 to 700 °C were compared with thermodynamic calculations. The Mn-based sorbent showed the best ability to achieve a low sulfur residual in the gas, especially at temperatures above 600 °C. Sorbents with Fe, Cu, and Mo gave SO₂ formation in the initial phase, but this could be avoided by a pre-reduction treatment of the sorbent material.     

Ir-Pt/C composite with high metal loading as a high-performance anti-reversal anode catalyst for proton exchange membrane fuel cells

Voltage reversal induced by hydrogen starvation can severely corrode the anode catalyst support and deteriorate the performance of proton exchange membrane fuel cells. A material-based strategy is the inclusion of an oxygen evolution reaction catalyst (e.g., IrO₂) in the anode to promote water electrolysis over harmful carbon corrosion. In this work, an Ir-Pt/C composite catalyst with high metal loading is prepared. The membrane-electrode-assembly (MEA) with 80 wt% Ir-Pt(1:2)/C shows a first reversal time (FRT) of up to 20 hours, which is about ten times that of MEA with 50 wt% Ir-Pt(1:2)/C does. Furthermore, the MEA with 80 wt% Ir-Pt(1:2)/C exhibits a minimum cell voltage loss of 6 mV@1 A/cm² when the FRT is terminated in 2 hours, in which the MEA with 50 wt% Ir-Pt(1:2)/C exhibits a voltage loss of 105 mV@1 A/cm². Further physicochemical and electrochemical characterizations demonstrate that the destruction of anode catalyst layer caused by the voltage reversal process is alleviated by the use of the composite catalyst with high metal loading. Hence, our results reveal that the combination of OER catalyst on the Pt/C with high metal loading is a promising approach to alleviate the degradation of anode catalyst layer during the voltage reversal process for PEMFCs.     

稳产国Ⅵ柴油并兼产喷气燃料技术方案的工业应用

介绍了浙江石油化工有限公司新建的3 Mt/a柴油加氢精制装置，其配套使用中国石化石油化工科学研究院有限公司开发的催化剂级配技术，并实施了可根据原料供应及市场产品需求情况灵活调整切换的2种生产技术方案。1 a的安稳生产运行结果表明:该装置以直馏柴油为主原料，通过分馏塔的馏分切割及其侧线抽出，实现了稳产国Ⅵ柴油并兼产喷气燃料技术方案的工业化应用；在实施以兼产喷气燃料为主的生产技术方案时，通过调整常一线柴油的掺炼量，不仅可以生产含硫量小于10.0 μg/g的精制柴油产品，同时兼产所得到的喷气燃料产品含硫量小于0.5 μg/g，赛波特颜色号值大于30；在实施主产精制柴油组分方案时，通过掺炼质量分数为20%~40%的催化柴油，并使所提炼得到的精制柴油组分含硫量小于6.0 μg/g的前提下，这些精制柴油组分产品既可直接作为满足国Ⅵ柴油产品出厂待售，也可作为柴油调和组分储存待用于产品的进一步优化。     

Manufacturing catalyst-coated membranes by ultrasonic spray deposition for PEMFC: Identification of key parameters and their impact on PEMFC performance

This study deals with the manufacturing of catalyst-coated membranes (CCMs) for newcomers in the field of coating. Although there are many studies on electrode ink composition for improving the performance of proton-exchange membrane fuel cells (PEMFCs), there are few papers dealing with electrode coating itself. Usually, it is a know-how that often remains secret and constitutes the added value of scientific teams or the business of industrialists. In this paper, we identify and clarify the role of key parameters to improve coating quality and also to correlate coating quality with fuel cell performance via polarization curves and electrochemical active surface area measurements. We found that the coating configurations can affect the performance of lab-made CCMs in PEMFCs. After the repeatability of the performance obtained by our coating method has been proved, we show that: (i) edge effects, due to mask shadowing - cannot be neglected when the active surface area is low, (ii) a heterogeneous thickness electrode produces performance lower than a homogeneous thickness electrode, and (iii) the origin and storage of platinum on carbon powders are a very important source of variability in the obtained results.     

Sputtered Ir–Ru based catalysts for oxygen evolution reaction: Study of iridium effect on stability

Magnetron sputtered low-loading iridium-ruthenium thin films are investigated as catalysts for the Oxygen Evolution Reaction at the anode of the Proton Exchange Membrane Water Electrolyzer. Electrochemical performance of 50 nm thin catalysts (Ir pure, Ir–Ru 1:1, Ir–Ru 1:3, Ru pure) is tested in a Rotating Disk Electrode. Corresponding Tafel slopes are measured before and after the CV-based procedure to compare the activity and stability of prepared compounds. Calculated activities prior to the procedure confirm higher activity of ruthenium-containing catalysts (Ru pure > Ir–Ru 1:3 > Ir–Ru 1:1 > Ir pure). However, after the procedure a higher activity and less degradation of Ir–Ru 1:3 is observed, compared to Ir–Ru 1:1, i.e. the sample with a higher amount of unstable ruthenium performs better. This contradicts the expected behavior of the catalyst. The comprehensive chemical and structural analysis unravels that the stability of Ir–Ru 1:3 sample is connected to RuO₂ chemical state and hcp structure. Obtained results are confirmed by measuring current densities in a single cell.     

Mechanism in chlorine-enhanced Pd catalyst for H2O2 in situ synthesis in electro-Fenton system

Palladium-based catalysts have been widely employed in the electro-Fenton process for in situ generation of H₂O₂. However, the process is still far from being practical on a large scale. In this work, a series of Cl_xFePd/γ-Al₂O₃/Al catalysts were prepared by a three-step-impregnation method. They exhibited excellent activity in H₂O₂ in situ synthesis and high efficiency in phenol degradation. The characterization results showed that Cl could assist in increasing the content of Pd⁰ and reducing the isoelectric point of catalysts, which led to the drastic promotion in the synthesis of H₂O₂. Theoretical calculations further demonstrated that Cl doping could facilitate the main reaction in H₂O₂ synthesis, as well as inhibit side reactions such as dissociation of the O O bond. Furthermore, kinetic models were proposed and fitted. A plausible reaction mechanism as well as degradation pathways were elaborated based on electron spin resonance and gas chromatography–mass spectrometry results. These findings illustrate the value of palladium-based Cl_xFePd/γ-Al₂O₃/Al catalysts for their application in the electro-Fenton process.     

Nitrogen-phosphorus co-functionalized reduced graphene oxide supported NiCoPd-CeOx nanoparticles as a highly efficient and stable catalyst for formic acid dehydrogenation

Formic acid (HCOOH, FA), a common liquid hydrogen storage material, has attracted tremendous research interest. However, the development of efficient, low-cost and high-stable heterogeneous catalyst for selective dehydrogenation of FA remains a major challenge. In this paper, a simple co-reduction method is proposed to synthesize nitrogen-phosphorus co-functionalized rGO (NPG) supported ultrafine NiCoPd-CeO_x nanoparticles (NPs) with a mean size of 1.2 nm. Remarkably, the as-prepared Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows outstanding catalytic activity for FA dehydrogenation, affording a high TOF value of 6506.8 mol H₂ mol Pd^?1 h^?1 at 303 K and a low activation energy of 17.7 kJ mol^?1, which is better than most of the reported heterogeneous catalysts, and can be ascribed to the combined effect of well-dispersed ultrafine NiCoPd-CeO_x NPs, modified Pd electronic structure, and abundant active sites. The reaction mechanism of dehydrogenation of FA is also discussed. Furthermore, the optimized Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows excellent stability over 10^th run with 100% conversion and 100% H₂ selectivity, which may provide more possibilities for practical application of FA system on fuel cells.