CuO-SiO2气凝胶@TiO2纳米纤维无牺牲剂光催化还原CO2

采用溶胶-凝胶法制备CuO-SiO2复合气凝胶,通过在气凝胶孔道内填充TiCl4,然后将其气相水解,得到了在CuO-SiO2气凝胶表面生长了高结晶度的TiO2纳米纤维(CuO-SiO2@TiO2),纤维直径～16 nm.通过XPS、UPS、UV-Vis DRS、荧光光谱(PL)等表征了材料的结构及光电性能.结果表明,制备的CuO-SiO2@TiO2对可见光有明显吸收,且荧光强度较商用TiO2(P25)大幅降低,光生电子-空穴对更加稳定.再在纳米纤维上负载CuO,所得CuO-SiO2@TiO2/CuO在可见光区的荧光强度进一步增强.以300 W氙灯为光源,分别以CuO-SiO2@TiO2及CuO-SiO2@TiO2/CuO为催化剂,无牺牲剂条件下光催化还原CO2,4 h后甲醇产率分别为1304.0及1589.0μmol/g-cat,转换频率(TOF)分别为0.038及0.046 h–1.循环实验表明,纳米纤维具有较好的光催化稳定性,经过4次光催化循环实验后,CuO-SiO2@TiO2/CuO的保留率～94％,甲醇产率可达1472.0μmol/g-cat,TOF为0.042 h–1.     

Reconstructed Water Oxidation Electrocatalysts: The Impact of Surface Dynamics on Intrinsic Activities

Electroreduction of small molecules such as H₂O, CO₂, and N₂ for producing clean fuels or valuable chemicals provides a sustainable approach to meet the increasing global energy demands and to alleviate the concern on climate change resulting from fossil fuel consumption. On the path to implement this purpose, however, several scientific hurdles remain, one of which is the low energy efficiency due to the sluggish kinetics of the paired oxygen evolution reaction (OER). In response, it is highly desirable to synthesize high-performance and cost-effective OER electrocatalysts. Recent advances have witnessed surface reconstruction engineering as a salient tool to significantly improve the catalytic performance of OER electrocatalysts. In this review, recent progress on the reconstructed OER electrocatalysts and future opportunities are discussed. A brief introduction of the fundamentals of OER and the experimental approaches for generating and characterizing the reconstructed active sites in OER nanocatalysts are given first, followed by an expanded discussion of recent advances on the reconstructed OER electrocatalysts with improved activities, with a particular emphasis on understanding the correlation between surface dynamics and activities. Finally, a prospect for clean future energy communities harnessing surface reconstruction-promoted electrochemical water oxidation will be provided.     

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.     

Prediction of Flooding in Packed Liquid-Liquid and High-Pressure Extraction Columns Using a Gaussian Process

Reliable prediction of flooding conditions is needed for sizing and operating packed extraction columns. Due to the complex interplay of physicochemical properties, operational parameters and the packing-specific properties, it is challenging to develop accurate semi-empirical or rigorous models with a high validity range. State of the art models may therefore fail to predict flooding accurately. To overcome this problem, a data-driven model based on Gaussian processes is developed to predict flooding for packed liquid-liquid and high-pressure extraction columns. The optimized Gaussian process for the liquid-liquid extraction column results in an average absolute relative error (AARE) of 15.23 %, whereas the algorithm for the high-pressure extraction column results in an AARE of 13.68 %. Both algorithms can predict flooding curves for different packing geometries and chemical systems precisely.     

致密砂岩油藏能量补充方式评价及优化

针对致密砂岩油藏大规模体积压裂开发后能量补充困难的问题,利用自主设计制作的大型人造三维岩心物理模型和物理模拟实验舱,开展致密砂岩油藏能量补充方式优化研究。实验结果表明:致密砂岩油藏压裂开发过程中,地层能量损耗严重,采取注水或注气的方式可有效进行能量补充;地层中裂缝规模越大,越有利于原油渗流,后续补充能量的传播范围越广,有助于进一步提高原油采收率;从提高驱油效率和扩大波及系数方面优选吞吐渗吸介质,CO₂均优于活性水,CO₂吞吐开发在矿场试验中取得了显著的增油效果,因此,CO₂吞吐作为一种有效的能量补充方式在致密油开发中展现了良好的应用前景。该文分析了致密砂岩储层水平井压裂开发的渗流规律,优选出致密砂岩储层大规模压裂开发后最佳渗吸介质,可为致密砂岩油藏开发设计提供重要的理论依据。     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Swapping catalytic active sites from cationic Ni to anionic F in Fe–F–Ni3S2 enables more efficient alkaline oxygen evolution reaction and urea oxidation reaction

Electrolysis of water for producing hydrogen instead of traditional fossil fuels is one of the most promising methods to alleviate environmental pollution and energy crisis. In this work, Fe and F ion co-doped Ni₃S₂ nanoarrays grown on Ni foam substrate were prepared by typical hydrothermal and sulfuration processes for the first time. Density functional theory (DFT) calculation demonstrate that the adsorption energy of the material to water is greatly enhanced due to the doping of F and Fe, which is conducive to the formation of intermediate species and the improvement of electrochemical performance of the electrode. The adsorption energy of anions (F and S) and cations (Fe and Ni) to water in each material was also calculated, and the results showed that F ion showed the most optimal adsorption energy of water, which proved that the doping of F and Fe was beneficial to improve the electrochemical performance of the electrode. It is worth noting that the surface of Fe–F–Ni₃S₂ material will undergo reconstruction during the process of water oxidation reaction and urea oxidation reaction, and amorphous oxides or hydroxides in situ would be formed on the surface of electrode, which are the real active species.     

Evaluation of physicochemical properties and microbial counts of raw and cooked low-fat patties added with eggplant powder prepared with different drying methods

Effects of different drying methods and different addition levels of eggplant (EP) on product quality of low-fat patties (LFPs) were investigated during storage. EP was dried in an oven dryer at 60 °C or a freeze dryer at −50 °C. LFPs were prepared by replacing with 1.5% soy protein isolate (SPI). Six treatments were used in this study: (1) control (CTL), without addition of EP; (2) reference (REF), 0.1% ascorbic acid; (3) O1, 0.25% oven-dried (OD) EP; (4) O2, 0.5% ODEP; (5) F1, 0.25% freeze-dried (FD) EP; and (6) F2, 0.5% FDEP. Redness (a*) and lightness (L*) values in LFPs added with EP were lower than those of others (p < 0.05) and decreased with increasing storage time. Yellowness (b*) values of cooked patties were increased during storage time (p < 0.05), with control having the highest value. The addition of EP or ascorbic acid into LFPs lowered microbial counts than control (p < 0.05). Thiobarbituric acid reactive substances (TBARS) was increased during storage, with REF having the lowest value, and patties added with EP had lower TBARS values than control during storage. Volatile basic nitrogen (VBN, mg%) contents of all patties also increased during storage time with O2 and F2 having lower values than control. Therefore, EP might have potential as a natural antioxidant in meat products during storage.     

Wavelength-dependent photoactivity of ZnxCd1−xS and ZnCo2O4/ZnxCd1−xS for H2 and H2O2 production

Zinc cadmium sulfide (Zn_xCd_1?xS) is a good photocatalyst for hydrogen evolution reaction (HER), but an optimum x (x_m) at which a maximum HER rate is reached varies from one report to another. In this work, we examine the effect of light wavelength, not only for the HER to H₂ in the presence of Na₂S and Na₂SO₃, but also for oxygen reduction reaction (ORR) without addition of any sacrifices. For the HER under a 365 and 420 nm LED lamp, the x_m were 0.9 and 0.7, respectively. For the HER under a 330 and 395–515 nm cut-off xenon lamp, the x_m were 0.7 and 0.5, respectively. For the ORR under a 420 nm cut-off halogen lamp, a maximum production of H₂O₂ was observed at x = 0.3. Furthermore, after 4% ZnCo₂O₄ loading, Zn_xCd_1?xS had an increased activity and stability, either for the HER or for the ORR. Through a (photo)electrochemical measurement, it is proposed that the photocatalytic activity of Zn_xCd_1?xS is determined by its light absorptivity and electron reactivity. The improved performance of n-type Zn_xCd_1?xS by p-type ZnCo₂O₄ is due to formation of a p-n junction, promoting the HER (ORR) on Zn_xCd_1?xS, and the sulfide (water) oxidation on ZnCo₂O₄. This work highlights that Zn_xCd_1-xS is a promising photocatalyst for H₂ and H₂O₂ production, respectively.     

Effects of multiple freeze–thaw cycles on meat quality,nutrients, water distribution and microstructure in bovine rumen smooth muscle

This study investigated the effect of 5 freeze–thaw cycles (freezing at −18°C for 12 h and then thawing at 4°C for approximately 12 h) on the meat quality, proximate composition, water distribution and microstructure of bovine rumen smooth muscle (BSM). As the number of freeze–thaw cycles increased, BSM pH, shear force, water content and protein content decreased by 3.06%, 35.50%, 14.49% and 21.11%, respectively, whereas BSM thawing loss, cooking loss, pressing loss, total aerobic count (TAC), ash content and fat content increased by 108.12%, 47.75%, 78.33%, 90.99%, 105% and 35.20%, respectively. The freeze–thaw cycles resulted in greater protein and lipid oxidation, as evidenced by a 36.46% reduction in the sulfhydryl content and a 209.06% and 338.46% increase in the carbonyl and malondialdehyde contents, respectively. Ice crystal formation disrupted the structural integrity of the muscle tissue. Low-field nuclear magnetic resonance results showed that the freeze–thaw cycles prolonged the relaxation times (T_2b, T₂₁ and T₂₂), indicating that immobile water shifted to free water, and consequently, free water mobility increased. After 3 freeze–thaw cycles, the decline in shear force slowed, the increase in thawing loss became accelerated, and the TAC approached the domain value (6 log colony-forming units/g). Therefore, the number of freeze–thaw cycles of smooth muscle during transport, storage and distribution should be controlled to 3 or fewer. The current results provide a theoretical basis and data support for the further utilisation and culinary processing of smooth muscle.