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.     

Structure engineering of amorphous P–CoS hollow electrocatalysts for promoted oxygen evolution reaction

Oxygen evolution reaction (OER) is a key process involved in many energy-related conversion systems. An ideal OER electrocatalyst should possess rich active sites and optimal binding strength with oxygen-containing intermediates. Although numerous endeavors have been devoted to the modification and optimization of transition-metal-based OER electrocatalysts, they are still operated with sluggish kinetics. Herein, an ion-exchange approach is proposed to realize the structure engineering of amorphous P–CoS hollow nanomaterials by utilizing the ZIF-67 nanocubes as the precursors. The precise structure control of the amorphous hollow nanostructure contributes to the large exposure of surface active sites. Moreover, the introduction of phosphorus greatly modifies the electronic structure of CoS₂, which is thus favorable for optimizing the binding energies of oxygenated species. Furthermore, the incorporation of phosphorus may also induce the formation of surface defects to regulate the local electronic structure and surface environment. As a result of this, such P–CoS hollow nanocatalysts display remarkable electrocatalytic activity and durability towards OER, which require an overpotential of 283 mV to afford a current density of 10 mA cm^?2, outperforming commercial RuO₂ catalyst.     

Investigation of fabrication of gas diffusion substrate for proton exchange membrane fuel cells

The gas diffusion substrate (GDS) is essential in the proton exchange membrane fuel cells. Its fabrication techniques affect the performance significantly and are worthy of investigation. In this study, a manufacturing process of the GDS is proposed to understand the formation process of GDS and promote its structure and performance more pertinently. Different states during the preparation process, raw carbon paper, pre-curing, curing, carbonation, and graphitization, are characterized and measured. Experimental and numerical methods are employed to determine the relationships between microstructure, transport, and mechanical performance variation with the fabricating processes. The results show that its porosity, average pore size, and effective diffusivity decrease first and increase after curing. These parameters after graphitization are lower than that of the carbon paper (CP). The electrical resistivity increases dramatically while pre-curing and decreases gradually after curing, carbonation, and graphitization, and it is much reduced after graphitization. Moreover, mechanical measurement results show that both the picks of tensile strength and flexural modulus occur after curing. Its tensile strength shows little change after graphitization compared to the initial paper's. In contrast, the flexural modulus is improved significantly.     

Synergistic effect of high-intensity ultrasound and β-cyclodextrin treatments on browning control in apple juice

This work evaluated the synergistic effects of combined high-intensity ultrasound (HIU) with β-cyclodextrin (β-CD) treatments on inhibiting browning of apple juice and explored the mechanism through simulation system. The combined treatment of 300 W HIU with 0.006 g mL⁻¹ β-CD had a synergistic impact on maintaining juice colour, resulting in a 39.06% reduction in browning degree, only a 36.64% decrease in total phenolic content, and a 17.82% reduction in PPO activity. The inhibition of enzymatic browning in simulated system revealed that HIU suppressed the enzyme (Polyphenol oxidase, PPO) and β-CD inhibited enzyme (PPO) and embedded substrate (polyphenol). The results of spectroscopic analysis showed that the particle-size distribution of PPO narrowed, the content of α-helix in the secondary structure increased, the fluorescence intensity increased, and the maximum wavelength was red-shifted after HIU and β-CD treatment. Changes in structure could further result in PPO activity loss. Hence, the combined treatment could synthetically alleviate the browning of apple juice.     

Cation and polyhedron substitution strategies: Effects on local crystal structure and on Bi3+ and Eu3+ co-doped inverse garnet phosphors’ luminescence property

Following the rapid growth of lightning technology, the development of red-emitting phosphors is effective for improving color temperature and color rendering index for w-LEDs devices. Herein, a single phased garnet phosphor with cation and polyhedron substitution modification was firstly prepared. For Mg₃Gd₂Ge₃O₁₂: Bi³⁺, Eu³⁺, the intensity has been remarkably improved by about 16% compared to the one without Bi³⁺ sensitization. The energy transfer mechanism is identified in this work. Based on cation and polyhedron substitution strategies, novel phosphors with different compositions were obtained and further modified the PL properties. With Lu³⁺ substitution, the bond lengths between Bi³⁺ ion and anion ligands are decreased and the site symmetry has been strengthened, which leads to a 21 nm blue shift when Lu³⁺ totally replaced Gd³⁺ ions. In addition, Lu³⁺ and [SiO₄] substitution strategies both effectively increased symmetric rigid structure, which leads to a significant improvement in thermal stability, indicating the samples own great potential in optical applications This work provides a new insight to synthesis red-emitting phosphors for warm white-LEDs.     

贵阳都市圈的空间结构分析与优化策略研究*

都市圈已经成为新型城镇化推进的主 要战略空间，在推进区域一体化发展中发挥着重 要作用。贵阳都市圈的建设对于西南地区的高质 量发展具有重要意义。基于空间相互作用理论， 研究通过建立城市综合质量评价指标体系、修 正引力模型、断裂点模型分析贵阳都市圈的空 间结构特征，结果表明贵阳都市圈呈现出核心 城市与周边城镇空间发展不均衡、强核心—弱 边缘的圈层式空间结构、圈层扩散及轴向放射 式的都市圈空间发展导向、距离核心城市40— 80 km断裂点区域发展滞后的空间结构特征。研 究发现贵阳都市圈仍处于初期发展阶段，核心 城市的发展能级受到生态环境及区域发展阶段 的影响，尚未形成对都市圈地区的全面带动。研 究提出需要进一步增强核心城市能级，积极培育次级中心城市，通过打造现代化产业体系、健全 交通网络强化都市圈内部联系，形成“核心—环网—放射状”的区域一体化都市圈空间结构。     

Design and synthesis of side-chain optimized poly(2,6-dimethyl-1,4-phenylene oxide)-g-poly(styrene sulfonic acid) as proton exchange membrane for fuel cell applications: Balancing the water-resistance and the sulfonation degree

Side-chain optimized poly (2,6-dimethyl-1,4-phenylene oxide)-g-poly (styrene sulfonic acid) (PPO-g-PSSA) is designed with balanced water-resistance and sulfonation degree. The PPO-g-PSSA is synthesized by controlled atom-transfer radical polymerization (ATRP) from brominated poly (2,6-dimethyl-1,4-phenylene oxide) (PPO-xBr) and ethyl styrene-4-sulfonate and followed by hydrolysis. A series of PPO-g-PSSA are prepared possessing different bromination degree (x) of PPO-xBr and polymerization degree (m) of the side-chains and the water-resistances of the fabricated membranes are investigated. The results show that a PPO-g-PSSA at relatively low x (x < 0.2) and high m (m > 4) exhibits good balance between the water-resistance and the sulfonation degree. Namely, it displays suitable proton conductivity with compromised water-resistance. Moreover, a maximum ion exchange capacity (IEC) of 3.24 mmol g^?1 is reached without the sacrifice of water-resistance. In addition, PPO-g-0.08PSSA-13 and PPO-g-0.14PSSA-4 are chosen characterized by thermogravimetric analysis, proton conductivities and mechanical properties. At 90% RH, the optimized PPO-g-0.08PPSA-13 possesses a proton conductivity of 37.9 mS cm^?1 at 40 °C and 45.5 mS cm^?1 at 95 °C, respectively.     

Time and space dependence of large-scale synthesis of colloidal particle with special morphology and tuneable polymer film architecture

This paper describes a facile method to control the morphology of polymer colloids and the architecture of polymer film via miniemulsion polymerization. By taking advantage of cyclization between the symmetrical diacrylate cross-linker hexamethylene diacrylate (HDDA) and the pendent vinyl in colloidal particles, the morphology of polymer colloids and the architecture of the after-formed polymer film were able to be well controlled by tuning the loading of cross-linker HDDA and crosslinking time. Four kinds of polymer colloid morphologies and four kinds of film architecture (honeycomb, close-packed, loose-packed, and enhanced-honeycomb) were characterized by TEM. The film formation mechanisms behind them were proposed based on the special and interesting results including Z-average size of the colloidal particles, Mc (molecular weight between crosslinking points) and mechanical properties of polymer film. Our results highly suggested that the morphology of polymer colloids and the polymer film architecture together determine the adhesive properties of the colloidal polymer film. The best of 180°-peel resistance, T-peel resistance and shear resistance of the polymer films were 138.12 N/25 mm, 40.98 N/25 mm and 25.72 N/cm² at 2.0 phm, 2.0 phm and 0.4 phm with the same crosslinking time of 90 min, respectively. The proposed method is promising to be scaled up for industrial production due to its well adaptability.     

Pore-scale study of effects of different Pt loading reduction schemes on reactive transport processes in catalyst layers of proton exchange membrane fuel cells

Reducing the Platinum (Pt) loading while maintaining the performance is highly desired for promoting the commercial use of proton exchange membrane fuel cells (PEMFCs). Different methods have been adopted to fabricate catalyst layers (CLs) with low Pt loading, including utilizing lower Pt/C catalysts (MA), mixing high Pt/C catalysts with bare carbon black particles (MB), and reducing CL thickness while maintaining high Pt/C ratio (MC). In this study, self-developed pore-scale model is adopted to investigate the performance of the three Pt reduction methods. It is found that MA shows the best performance while MB shows the worst. Then, effects of Pt dispersion are further explored. The results show that denser Pt sites will result in higher local oxygen flux and thus higher local transport resistance. Therefore, MA method, which shows the better Pt dispersion, leads to improved performance. Third, CLs with quasi-realistic structures are investigated. Higher tortuosity resulting from the random pores produces higher bulk resistance along the thickness direction, while MA still exhibits the best performance. Finally, improved CL structures are investigated by designing perforated CL structures. It is found that adding perforations can significantly reduce the bulk transport resistance and can improve the CL performance. It is demonstrated that CL structure plays important roles on performance, and there are still huge potentials to further improve CL performance by increasing Pt dispersion and optimizing CL structures.     

起·承·转·合 ——解读巍宝山长春洞空间布局的结构章法

长春洞是巍宝山保存最完整的宫 观，虽占地不到两亩①，却在有限的空间中 创造出九楼十院的空间格局。本文以长春洞 空间布局序列为研究对象，从知觉体验的 连续性入手，提出了空间变化对参观者情感 的影响，论述了在建筑空间布局序列中参观 者知觉体验逐层递进的控制机制，探讨了以 “起、承、转、合”为结构，以“知觉体验”为 章法的动态空间布局设计手法，希望为道教 建筑空间与其他超越日常的精神空间的研 究提供启示。