Morphologically controlled synthesis of 1-dimensional selenium dioxide and study of its application as catalyst for diesel fuel additive

In this research work, selenium dioxide (SeO₂) nanorods have been prepared by a solvothermal method in which a strong reducing agent (NaBH₄) was used to reduce precursor salt into SeO₂ nanorods. X-ray diffraction (XRD) technique was applied to observe the crystal structure which confirmed its tetragonal geometry. Moreover, morphology and particle size were studied by scanning electron microscopy (SEM). SEM fully described the 1-dimensional morphology of SeO₂ nanorods which then arranged themselves to create a 3-dimensional flower-like structure with an average particle size of 50 nm. Also, the catalytic activity of SeO₂ nanorods as diesel-additive was studied by defining different parameters such as fire and flash points, calorific value, cloud and pour points, specific gravity, and kinematic viscosity. Subsequently, SeO₂ nanorods proved to be an excellent diesel additive due to higher total heat content and lower value of kinematic viscosity which enhances the better performance of the diesel engine.     

Blocking the defect sites on ultrathin Pt nanowires with Rh atoms to optimize the reaction path toward alcohol fuel oxidation

Anodic electrocatalyst plays the core role in direct alcohol fuel cells (DAFCs), while traditional Pt-catalysts suffer from limited catalytic activity, high over potential and severe CO poisoning. Herein, by selectively depositing Rh atoms on the defective-sites of Pt nanowires (NWs), we developed a new Pt@Rh NW electrocatalyst that exhibited enhanced electrocatalytic performance for both methanol oxidation (MOR) and ethanol oxidation (EOR). Both cyclic voltammetry (CV) and in-situ infrared spectroscopy revealed that the presence of Rh atoms suppressed the generation of poisonous intermediates and completely oxidized alcohols molecule into CO₂. Atomic resolusion spherical aberration corrected high-angle annular dark field scanning transmission electron microscopy (CS-HAADF-STEM) and energy-dispersive X-ray spectroscopy (EDS) mapping analysis revealed that Rh atoms were primarily deposited on the defective sites of Pt NWs. Meanwhile, the presence of Rh atoms also modified the electronic state of Pt atoms and therefore lowered the onset potential for alcohols oxidation potential. This work gives the first clear clue on the role of the defective sites of Pt nanocatalyst poisoning, and propose that selectively blocking these sites with trace amount of Rh is an effective strategy in designing advantageous electrocatalysts.     

大豆脲酶诱导碳酸钙沉淀的多因素影响分析

本文探究了多个影响因素对大豆脲酶诱导碳酸钙沉淀(SICP)的影响,以优选出主要影响因素并提供其最佳范围。首先分析了脲酶浓度和温度对脲酶活性的影响;之后通过正交实验设计,进行25种工况的SICP水溶液实验,研究不同因素组合下Ca²⁺利用率的变化规律;最后借助扫描电子显微镜观测不同工况下生成碳酸钙的形态。结果表明:低温有利于脲酶的保存及活性发挥,5 ℃时脲酶活性能保持21 d以上;同一温度下,脲酶浓度越大,脲酶初始活性越高,脲酶完全失活所需时间越短。pH值、脲酶与胶结液体积比是影响Ca²⁺利用率的主要因素。为达到较高的Ca²⁺利用率,脲酶和胶结液最佳体积比为1,氯化钙与尿素最佳浓度比为1.5,Ca²⁺最佳浓度为1 mol/L。当脲酶浓度较低时生成的六面体状碳酸钙较多;随着脲酶浓度的增大,所沉淀的碳酸钙向球形转变。大豆中富含的天冬氨酸是控制碳酸钙形态的重要因素。     

Proton exchange membrane prepared by blending polybenzimidazole with poly (aminophosphonate ester)

In this article, we report a new amorphous-crystalline polymer blend system consisting of poly (4, 4′-diphenylether-5, 5′-bibenzimidazole) (OPBI) and poly (aminophosphonate ester) (PAPE) polymers, the membranes of which were fabricated using the solution blending route. A series of blend membranes at different ratios were prepared and systematically analysed for chemical interactions, morphological changes and their physico-chemical properties studied for use as proton exchange membrane. While FT-IR spectroscopy established the hydrogen bonding interactions between N–H of OPBI and phosphonate ester group of PAPE, X-ray diffraction studies revealed the development of crystallinity in the membrane matrix. Interestingly, the gradual induction of crystallinity in an amorphous OPBI matrix was found to influence the properties of the blend membranes favourably. For instance, the blend membrane containing 25 wt% PAPE in OPBI matrix displayed the maximum property enhancement in terms of storage modulus, glass transition temperature (T_g), phosphoric acid (PA) doping level (37 mol/OPBI repeat unit) and most importantly proton conductivity (0.135 S/cm at 180 °C) which is almost twice the value for pristine OPBI (0.05 S/cm at 180 °C) under identical conditions. Although improved properties were observed at other blend ratios as well, the studies ascertain that the membrane with 25 wt% PAPE was found to be the threshold ratio up to which properties increase and beyond which i.e. at >25 wt% PAPE, there is a decrement in properties like mechanical stability and proton conductivity. An important reason for this was attributed to the creation of a right balance of amorphous and crystalline domains and appropriate intra and inter-polymer hydrogen bonding interactions in the matrix of 75/25 (OPBI/PAPE) blend membrane.     

Electrodeposition of nanostructured catalysts for electrochemical energy conversion: Current trends and innovative strategies

This review discusses the latest advances in electrodeposition of nanostructured catalysts for electrochemical energy conversion: fuel cells, water splitting, and carbon dioxide electroreduction. The method excels at preparing efficient and durable nanostructured materials, such as nanoparticles, single atom clusters, hierarchical bifunctional combinations of hydroxides, selenides, phosphides, and so on. Yet, in most cases, chemical composition cannot be decoupled from catalyst morphology. This compromises the rational design of electrodeposition procedures because performance indicators depend on both morphology and surface chemistry. We expect electrodeposition will keep unraveling its potential as the preferred method for electrocatalyst synthesis once a deeper understanding of the electrochemical growth process is combined with complex chemistries to have control of the morphology and the surface composition of complex (bifunctional) electrocatalysts.     

Synthesis and characterization of BaGa2O4 and Ba3Co2O6(CO3)0.6 compounds in the search of alternative materials for Proton Ceramic Fuel Cell (PCFC)

BaGa₂O₄ and Ba₃Co₂O₆(CO₃)_0.6 compounds were studied as electrolyte and cathode materials for Proton Ceramic Fuel Cells (PCFC), respectively. Not only BaGa₂O₄ rapidly reacts with atmospheric H₂O and CO₂ and leads to a progressive material decomposition, but it does not present real hydration properties in normal conditions of pressure. On the other hand, the basic cobalt oxocarbonate Ba₃Co₂O₆(CO₃)_0.6 exhibits an interesting tendency for weight uptake and formation of hydrogencarbonate groups in moist heating/cooling conditions. This material was therefore considered for complementary studies in order to confirm its potential use as mixed proton-electron conductor, taking into account the ordered intergrowth of carbonates and face sharing Co-octahedra columns forming a pseudo-one-dimensional structure. Some preliminary results concerning electrochemical properties of the barium cobalt oxocarbonate as a PCFC cathode are also described and show at the moment modest performance, possibly related to a hydrated/carbonated surface layer contribution and/or the lack of electron percolation within the electrode layer.     

Environmental remediation by hydroxyapatite: Solid state synthesis utilizing waste chicken eggshell and adsorption experiment with Congo red dye

This study reports the adsorption efficacy of hydroxyapatite (HAp) for removing Congo Red (CR) dye from aqueous solution. HAp was synthesized utilizing chicken eggshell as a precursor of Ca source. Solid state synthesis method was implemented which comprised calcination at 950 °C (E-HAp950). XRD analysis confirmed the formation of bi-phasic HAp with 15.5% of β-TCP. Elemental composition was evaluated by XPS and EDX analysis. FESEM analysis revealed the particles are of plate and spherical shaped also confirmed by the TEM images. DLS particle size, zeta potential, BET surface area and point of zero charge were also evaluated. Adsorption efficacy of E-HAp950 for removing CR was evaluated by batch adsorption experiment. Maximum adsorption capacity (q_max) was found to be 9.64 mgg⁻¹ which was best explained by the non-linear fitting (R² = 0.98) of Langmuir isotherm. Adsorption kinetics profusely followed pseudo second order kinetic model (R² = 0.999) with q_{e (experimental)} being very much closer to q_{e (calculative)} for this model. Thus, hydroxyapatite prepared by utilizing eggshell waste through solid state method has the potential to remove toxic dyes.     

Solar-Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

Photothermal CO₂ reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium-modified carbon-supported cobalt (K⁺−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus-pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K⁺−Co−C catalyst shows a record-high photothermal CO₂ hydrogenation rate of 758 mmol g_cat⁻¹ h⁻¹ (2871 mmol g_Co⁻¹ h⁻¹) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO₂ reduction reactions. We further demonstrate with this catalyst effective CO₂ conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.     

Carbon-Based Electrocatalysts for Acidic Oxygen Reduction Reaction

Oxygen reduction reaction (ORR) is vital for clean and renewable energy technologies, which require no fossil fuel but catalysts. Platinum (Pt) is the best-known catalyst for ORR. However, its high cost and scarcity have severely hindered renewable energy devices (e.g., fuel cells) for large-scale applications. Recent breakthroughs in carbon-based metal-free electrochemical catalysts (C-MFECs) show great potential for earth-abundant carbon materials as low-cost metal-free electrocatalysts towards ORR in acidic media. This article provides a focused, but critical review on C-MFECs for ORR in acidic media with an emphasis on advances in the structure design and synthesis, fundamental understanding of the structure-property relationship and electrocatalytic mechanisms, and their applications in proton exchange membrane fuel cells. Current challenges and future perspectives in this emerging field are also discussed.     

Bulk-like Pt(100)-oriented Ultrathin Surface: Combining the Merits of Single Crystals and Nanoparticles to Boost Oxygen Reduction Reaction

Single crystal surfaces with highly coordinated sites very often hold high specific activities toward oxygen reduction reaction (ORR) and others. Transposing their high specific activity to practical high-surface-area electrocatalysts remains challenging. Here, ultrathin Pt(100) alloy surface is constructed via epitaxial growth. The surface shows 3.1–6.9 % compressive strain and bulk-like characteristics as demonstrated by site-probe reactions and different spectroscopies. Its ORR activity exceeds that of bulk Pt₃Ni(100) and Pt(111) and presents a 19-fold increase in specific activity and a 13-fold increase in mass activity relative to commercial Pt/C. Moreover, the electrochemically active surface area (ECSA) is increased by 4-fold compared to traditional thin films (e.g. NSTF), which makes the catalyst more tolerant to voltage loss at high current densities under fuel cell operation. This work broadens the family of extended surface catalysts and highlights the knowledge-driven approach in the development of advanced electrocatalysts.