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.     

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.     

水力空化改质对重质原油沥青质及性质的影响

利用水力空化过程产生局部的高温、高压、高射流以及强大的剪切力等极端化学物理条件改质处理沙特重质原油，试验结果表明：沙特重质原油经过水力空化改质后粘度由13.61降低至7.22mm2/s，残碳由7.16%降低至6.48%，实沸点蒸馏后减压渣油降低1个百分点。进一步采用APPI FT-IR MS、XRD、FT-IR、SEM和粒度分布等技术研究了水力空化改质对沙重原油分子组成，沥青质团聚体微晶结构、沥青质胶束粒径分布、沥青质官能团、沥青质形貌等方面的影响，从分子角度阐述空化改质重油的机理。研究结果表明：水力空化改质后沙重原油分子量分布、芳烃类化合物缔合作用变小；沥青质对低DBE化合物吸附性能降低；沥青质团聚体微晶结构更加松散；沥青质胶束粒度分布降低；沥青质分子相互团聚作用力减弱。进一步考察了水力空化改质前后减压渣油延迟焦化性能，改质处理后焦炭产率降低1.85个百分点，液体收率和气体产率分别增加1.52和0.33个百分点，水力空化改质对沥青质性质、结构特点的改善能够有效的提高其加工性能。     

海上热采防砂封隔器研制与室内试验

海上稠油热采开发过程中,通常采用蒸汽吞吐的方式进行原油开采。为满足稠油热采长效密封要求,研制了HPHT-215型热采防砂封隔器。封隔器胶筒采用特制的氟硅基复合材料+玻璃纤维网结构,并开展了材料性能评价测试。通过有限元分析和室内胶筒组合测试,对胶筒材料和组合结构进行了评价优化。室内全尺寸整机测试表明:封隔器能够满足耐温350 ℃、耐压21 MPa密封性能要求,并开展了高低温多轮次密封性能评价测试。该型热采防砂封隔器的研制成功,为海上稠油蒸汽吞吐多轮次开发提供了保障,具有广泛的应用前景。     

Effect of nickel concentration on biohydrogen production: Organic solid waste vs. glucose

In recent years, alternative renewable energy generation sources have been investigated, highlighting the dark fermentation process due to it’s potential to obtain hydrogen-rich gas, which can be used as an energy source. Different trace metals intervene in this biological process. Nickel is one of the most important because it is a component of the [Ni–Fe] hydrogenase enzyme that catalyzes the oxidation of H₂ in numerous bacteria. The aim of this study was to evaluate the effect of nickel on biohydrogen production from organic solid waste (OSW). The experimental setup was carried out in batch tests using OSW as the substrate, glucose as a reference compound and the valuation of Ni²⁺ doses on the operation in a Sequencing Batch Reactor. The results of the batch tests showed that when using glucose as a substrate, 2 mg Ni²⁺/g VS_inoculum generated the highest hydrogen production (774 ± 7.3 mL H₂/L/d) and highest yield (55.8 ± 3.4 mL H₂/g of glucose), which was 34.4% higher than the control. Testing of different concentrations of nickel using OSW as a carbon source showed that the highest production was obtained without Ni²⁺ addition since the nickel concentration in the residue was 0.17 ± 0.06 mgNi/gVS; consequently, hydrogen production was not affected by the lack of Ni. The addition of 0.5 mg Ni²⁺/g VS_inoculum decreased acetate and butyrate production and increased caproate production.     

Rare earth metals co-doped ZnO/CNTs composite as high performance photocatalyst for hydrogen production from water_triethanolmine mixture

This study investigated the zinc oxide (ZnO) based heterojunction photocatalysts for improved hydrogen production from water splitting. A sol-gel route was adopted to produce terbium (Tb) and samarium (Sm) co-doped ZnO/CNTs composites where CNTs worked as a support material. The built-in redox couples of lanthanides in co-doped TS-ZnO/CNTs composite showed higher hydrogen evolution activity than Sm doped (Sm-ZnO/CNTs) and Tb doped (Tb–ZnO/CNTs) photocatalysts. When triethanolamine was utilized as a sacrificial agent, the TS-ZnO/CNTs photocatalyst result in a remarkable hydrogen evolution rate of 2683 molh^?1g^?1 under visible light illumination. The optimum photocatalyst also showed high stability over five successive hydrogen evolution cycles. The better hydrogen evolution rate with TS-ZnO/CNTs was referred to its fine particle size, high reactive surface area, small optical band gap, suppressed reunification of charge carriers and built-in redox couples. The photocatalytic mechanism, involved in water splitting with TS-ZnO/CNTs photocatalyst, is also deduced in this study. This study can stimulate the attempts towards construction of lanthanides based co-doped semiconductor photocatalysts for efficient hydrogen evolution.     

Plasma-assisted CO2 reforming of methane over Ni-based catalysts: Promoting role of Ag and Sn secondary metals

Carbon dioxide (CO₂) and methane (CH₄) are the primary greenhouse gases (GHGs) that drive global climate change. CO₂ reforming of CH₄ or dry reforming of CH₄ (DRM) is used for the simultaneous conversion of CO₂ and CH₄ into syngas and higher hydrocarbons. In this study, DRM was investigated using Ag–Ni/Al₂O₃ packing and Sn–Ni/Al₂O₃ packing in a parallel plate dielectric barrier discharge (DBD) reactor. The performance of the DBD reactor was significantly enhanced when applying Ag–Ni/Al₂O₃ and Sn–Ni/Al₂O₃ due to the relatively high electrical conductivity of Ag and Sn as well as their anti-coke performances. Using Ag–Ni/Al₂O₃ consisting of 1.5 wt% Ag and 5 wt% Ni/Al₂O₃ as the catalyst in the DBD reactor, 19% CH₄ conversion, 21% CO₂ conversion, 60% H₂ selectivity, 81% CO selectivity, energy efficiency of 7.9% and 0.74% (by mole) coke formation were achieved. In addition, using Sn–Ni/Al₂O₃, consisting of 0.5 wt% Sn and 5 wt% Ni/Al₂O₃, 15% CH₄ conversion, 19% CO₂ conversion, 64% H₂ selectivity, 70% CO selectivity, energy efficiency of 6.0%, and 2.1% (by mole) coke formation were achieved. Sn enhanced the reactant conversions and energy efficiency, and resulted in a reduction in coke formation; these results are comparable to that achieved when using the noble metal Ag. The decrease in the formation of coke could be correlated to the increase in the CO selectivity of the catalyst. Good dispersion of the secondary metals on Ni was found to be an important factor for the observed increases in the catalyst surface area and catalytic activities. Furthermore, the stability of the catalytic reactions was investigated for 1800 min over the 0.5 wt% Ag-5 wt% Ni/Al₂O₃ and 0.5 wt% Sn-5 wt% Ni/Al₂O₃ catalysts. The results showed an increase in the reactant conversions with an increase in the reaction time.     

掺合料对超高性能水泥基装饰材料性能的影响

将重钙粉与偏高岭土以不同的比例混合并替代白水泥，制备超高性能水泥基装饰材料,研究两者掺入比例变化对超高性能水泥基装饰材料工作性能、力学性能及自收缩的影响，采用SEM扫描电镜观察28 d龄期后试件内部微观形貌，研究表明，随着重钙粉与偏高岭土比例的增大，试件的致密程度和强度先增后减，其中B9-9的28 d抗压与抗折强度可以达到120.6 MPa与42.9 MPa，且工作性、收缩性能良好、内部结构致密。