Template‐Free Synthesis of Porous Fe3O4/SiOC(H) Nanocomposites with Enhanced Catalytic Activity

We present a template‐free synthesis of Fe₃O₄/SiOC(H) nanocomposites with in situ formed Fe₃O₄ nanoparticles with a size of about 50 nm embedded in a nanoporous SiOC(H) matrix obtained via a polymer‐derived ceramic route. Firstly, a single‐source precursor (SSP) was synthesized by the reaction of allylhydridopolycarbosilane (AHPCS) with Fe‐acetylacetonate [Fe(acac)₃] at 140°C. The SSP was heat‐treated at 170°C to generate Fe₃O₄ nanocrystals in the cross‐linked polymeric matrix. Subsequently, the SSP was pyrolyzed at 600°C–700°C in argon atmosphere to yield porous Fe₃O₄/SiOC(H) nanocomposites with the high BET surface area up to 390 m²/g, a high micropore surface area of 301 m²/g, and a high micropore volume of 0.142 cm³/g. The Fe‐free SiOC(H) ceramic matrix derived from original AHPCS is nonporous. The in situ formation of Fe₃O₄ nanoparticles embedded homogeneously within a nanoporous SiOC(H) matrix shows significantly enhanced catalytic degradation of xylene orange in aqueous solution with H₂O₂ as oxidant as compared with pure commercial Fe₃O₄ nanoparticles.     

Effect of additives on porosity of alumina materials obtained by freeze casting

The influence of two different additives, glycerol and polyvinyl alcohol (PVA), on the rheological behaviour and freeze casting performance of 35?vol.-% aqueous alumina suspensions is studied. Suspensions with PVA were prepared by either mixing all the components together or adding the PVA in a second step on the dispersed slurry. Although the slight increase in viscosity suggests that competitive adsorption occurs, the microstructure seems not to change depending on the order of addition of additives. Considering its lower molecular weight, glycerol provides lower viscosity, and as a consequence of its cryoprotective character, sintering leads to smaller pore size, being the porosity 35% for an added content of 10?wt-% with respect to solids. In the case of PVA, contents of 2?wt-% are enough to obtain solid firm bodies with a porosity of 48%. The porosity and the size of the pores decrease with increasing concentration of PVA.     

Water‐based freeze casting: Adjusting hydrophobic polymethylsiloxane for obtaining hierarchically ordered porous SiOC

The hydrophobic properties of methyl poly siloxane (MK) were pushed into the “hydrophilic” range by cross‐linking it with (3‐aminopropyl)triethoxysilane (APTES) and subsequent pyrolysis to enable water‐based freeze casting. Filler properties are investigated by varying the ratios of MK to APTES (1:1, 1:2, 1:3, 1:4, 1:5), and pyrolysis temperatures (400°C, 500°C, 600°C) for the purpose of determining an optimal set of characteristics for freeze casting. Additionally, filler selection for this purpose is facilitated by analysis of zeta potential values and vapor adsorption. It was found that water‐based freeze casting with hybrid fillers, followed by a pyrolysis step (600°C‐700°C), leads to a SiOC ceramic monolith with a lamellar pore morphology and a hierarchically ordered micro/meso/macropore structure. Samples pyrolyzed at 1000°C contain mesopores, having a SSA as high as 51.6 m²/g. The hierarchically porous structure is very promising for applications involving gas or liquid transportation.     

Fabrication of porous silica with controllable and tunable porosity via freeze casting

Porous ceramics offer unique properties that can bring advances to many application areas. The freeze-casting process has a strong potential for fabricating porous ceramics; however, the effects of process parameters on part porosity must be well understood for scalable manufacturing via freeze casting. This paper presents an experimental analysis of the freeze-casting process that correlates the freeze-casting parameters with pore characteristics. A full-factorial design of experiments is conducted on a unidirectional freeze-casting testbed using silica as the ceramic material and camphene as the solvent. The effects of solid loading, particle size, cooling temperature, and the distance from the cooling surface on porosity characteristics are evaluated. The fabricated samples are cross-sectioned vertically and horizontally and imaged using scanning electron microscopy. Image processing is used to obtain the porosity characteristics of areal porosity, pore size, pore shape, and pore orientation. The capability to steer the pore orientation is also demonstrated through bidirectional freezing experiments supported by a finite-element model. As a result, a quantitative understanding of the effects of freeze-casting process parameters on porosity characteristics is gained for the silica–camphene system. These results and the presented approach can be used for reproducible manufacture of porous ceramics with controlled porosity.     

Structural Design of Polymer‐Derived SiOC Ceramic Aerogels for High‐Rate Li Ion Storage Applications

SiOC ceramic aerogels with different porosity, pore size, and specific surface area have been synthesized through the polymer‐derived ceramic route by modifying the synthesis parameters and the pyrolysis steps. Preceramic aerogels are prepared by cross‐linking a linear polysiloxane with divinylbenzene (DVB) via hydrosilylation reaction in the presence of a Pt catalyst under highly diluted conditions. Acetone and cyclohexane are used as solvent in our study. Wet gels are subsequently supercritically dried with CO₂ to get the final preceramic aerogels. The SiOC ceramic aerogels are obtained after a pyrolysis treatment at 900°C in two different atmospheres: pure Ar and H₂ (3%)/Ar mixtures. The nature of the solvent has a profound influence of the aerogel microstructure in terms of porosity, pore size, and specific surface area. Synthesized SiOC ceramic aerogels have similar chemical compositions irrespective of processing conditions with ~40 wt% of free carbon distributed within remaining mixed SiOC matrix. The BET surface areas range from 215 m²/g for acetone samples to 80 m²/g for samples derived from cyclohexane solvent. The electrochemical characterization reveals a high specific reversible capacity of more than 900 mAh/g at a charging rate of C (360 mA/g) along with a good cycling stability. Samples pyrolyzed in H₂/Ar atmosphere show a high reversible capacity of 200 mAh/g even at a high charging/discharging rate of 20 C. Initial capacities were recovered after whole cycling procedure indicating their structural stabilities resisting any kind of exfoliations.     

Fabrication of polymer-derived ceramics with hierarchical porosities by freeze casting assisted by thiol-ene click chemistry and HF etching

The freeze casting technique assisted with cryo thiol-ene photopolymerization is successfully employed for the fabrication of macroporous polymer-derived silicon oxycarbide with highly aligned porosity. It is demonstrated that the free radical initiated thiol-ene click reaction effectively cross-linked the vinyl-containing liquid polysiloxanes into infusible thermosets even at low temperatures. Furthermore, mixed solution- and suspension-based freeze casting is employed by adding silica nanopowders. SiOC/SiO₂ foams with almost perfect cylindrical shapes are obtained, demonstrating that the presence of nano-SiO₂ does not restrict the complete photoinduced cross-linking. The post-pyrolysis HF acid treatments of produced SiOC monoliths yields hierarchical porosities, with SiOC/SiO₂ nanocomposites after etching demonstrating the highest specific surface area of 494 m²/g and pore sizes across the macro-, meso- and micropores ranges. The newly developed approach gives a versatile solution for the fabrication of bulk polymer-derived ceramics with controlled porosity.     

The formation and catalytic activity of silver nanoparticles in aqueous polyacrylate solutions

Silver nanoparticles (AgNPs) have been synthesized in the presence of polyacrylate through the reduction of silver nitrate by sodium borohydride in aqueous solution. The AgNO3 and polyacrylate carboxylate group concentrations were kept constant at 2.0 × 10^–4 and 1.0 × 10^–2 mol·L^–1, respectively, while the ratio of [NaBH₄]/[AgNO₃] was varied from 1 to 100. The ultraviolet-visible plasmon resonance spectra of these solutions were found to vary with time prior to stabilizing after 27 d, consistent with changes of AgNP size and distribution within the polyacrylate ensemble occurring. These observations, together with transmission electron microscopic results, show this rearrangement to be greatest among the samples at the lower ratios of [NaBH₄]/[AgNO₃] used in the preparation, whereas those at the higher ratios showed a more even distribution of smaller AgNP. All ten of the AgNP samples, upon a one thousand-fold dilution, catalyze the reduction of 4-nitrophenol to 4-aminophenol in the temperature range 283.2–303.2 K with a substantial induction time being observed at the lower temperatures.

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The cavitation development of poly(4-methyl-1-pentene) casting films studied by in situ small angle X-ray scattering

In this paper, the on-line small angle X-ray scattering/wide-angle X-ray scattering (SAXS/WAXS) characterization method was adopted to study the morphology evolution of poly(4-methyl-1-pentene) casting films during stretching. In this process, the lamellae structure was destroyed. And “bridge structure” was generated in the amorphous region. The scattering pattern changed obviously before and after cavities orientation. Stretching temperature and stretching speed mattered for the size of micropores. Low temperature helped generate more and larger voids. The faster stretching speed can improve the generation of cavities, enlarged cavitation number and helped its reorientation. These results provide the basic knowledge of how to produce poly(4-methyl-1-pentene) microporous membranes with high electrochemical performance.     

WO3/HMS催化剂多相催化氧化环戊烯合成戊二醛

以(NH4)2WO4为钨源制备的WO3/HMS分子筛为催化剂,过氧化氢为氧化剂,考察了在环戊烯氧化制备戊二醛的多相催化反应中反应时间、反应温度、催化剂质量、溶剂用量和氧化剂质量分数等因素对戊二醛收率的影响。筛选出WO3/HMS催化环戊烯(CPE)合成戊二醛反应的适宜工艺条件:n(H2O2)∶n(W)∶n(CPE)=2∶0.025∶1,V(t-BuOH)∶V(CPE)=8∶1,反应温度为35℃,反应时间为30 h。戊二醛的收率可达67%。     

Ni/Al2O3-MxOy催化剂催化松香加氢的催化性能及产物组成

研究了Ni/Al2O3-MxOy,催化剂催化松香氢化反应的催化性能,结果表明Ni/Al2O3-MxOy催化剂催化松香氢化具有较好的催化性能,枞酸转化率可达98%以上,氢化产物达到国家普通氢化松香(特级)标准.产物主要组分与Pd/C催化剂催化所得的氢化产物基本相同.     

微波诱导Fe3O4/AC催化氧化降解邻苯二甲酸二甲酯

为了有效地提高活性炭在微波场中的催化活性和分离性,采用化学共沉淀法制备了磁性四氧化三铁/活性炭（Fe₃O₄/AC）催化剂,并结合微波辐射技术用于催化氧化降解水中邻苯二甲酸二甲酯（DMP）。利用BET、扫描电镜/能谱（SEM/EDS）、X射线衍射（XRD）、X射线光电子能谱（XPS）、红外光谱（FTIR）和振动样品磁强计（VSM）等手段对催化剂的微观结构、形貌和磁性能进行了表征。研究了不同反应体系对DMP的降解率及反应动力学的影响,探讨了催化剂用量、微波辐射功率和溶液初始pH等因素对微波诱导Fe₃O₄/AC催化氧化降解DMP的影响,考察了催化剂的重复使用性能。结果表明,所制备的铁氧化物主要以Fe₃O₄为主,并已成功负载于活性炭上。Fe₃O₄/AC具有超顺磁性,饱和磁化强度为21.2emu/g,可通过外加磁场作用快速地从溶液中分离出来。微波诱导催化反应体系对DMP的降解率大于单独吸附或单纯微波辐射反应体系,且反应速率均符合一级反应动力学。催化剂用量越多,降解率越高;微波辐射功率的增加可以提高降解效率;溶液初始pH对DMP的降解率影响非常显著,随着pH的增大,降解率明显提高。Fe₃O₄/AC具备良好的催化活性及稳定性,循环使用5次后DMP的降解率仍保持在83.5%。通过气相色谱-质谱联用仪（GC-MS）分析,推断DMP在微波诱导Fe₃O₄/AC催化体系中的降解主要包括水解、异构化、羟基化、甲酸甲酯基的脱落和苯环三取代及苯环开环等5个途径。     

Catalytic activity during the preparation of PE/clay nanocomposites by in situ polymerization with metallocene catalysts

Catalytic activity during the formation of polyethylene (PE)/clay nanocomposites by in situ polymerization with metallocenes was studied. Ethylene polymerization was carried out with the homogeneous metallocene in the presence of the clay particles and using the clay‐supported metallocene catalyst. It was found that the catalytic activity of the homogeneous metallocene does not decrease in the presence of the clay particles and only a slight decrease of activity occurs using the clay‐supported catalyst. The modification of the clay with MAO cocatalyst as well as its intercalation with ODA surfactant were found to play an important role during the in situ formation of the PE/clay nanocomposite. ODA‐intercalated clay apparently facilitates the activation and monomer insertion processes on zirconocene centers located in internal sites of the clay structure. Although metallocene supported on MAO‐treated clay exhibited somewhat lower catalytic activity than that supported directly on the ODA‐intercalated clay, both systems favored the production of PE nanocomposites containing highly exfoliated clay particles. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Uniform dispersion of Ni nano particles in a carbon based catalyst for increasing catalytic activity for CH4 and H2 production by hydrothermal gasification

A carbon based nickel (Ni) catalyst was prepared by ion exchange method in which a large amount of Ni is dispersed as almost uniform nano particles. The method ion exchanges the ion exchangeable sites in an ion exchange resin with Ni followed by carbonization at 500 °C. Two different catalysts were prepared by ion exchanging Ni from an aqueous solution containing same amount of Ni ion concentration but at different pH of the solution. The amount of Ni ion exchanged in both cases was about 15%. The metal load after carbonization was about 47% and 46% in the two catalysts, respectively. The XRD pattern and TEM images of the catalysts showed that Ni particles in NiWB500 (pH = 8.8) were bigger in size in comparison to the Ni particles in NiLG500 (pH = 9.4). The BET surface area was 178 and 183 m²/g, respectively. The catalytic hydrothermal gasification (CHTG) experiments at 350 °C, 20 MPa, and 50 h⁻¹ LHSV for 50 h with organic water containing 0.2% and 2% TOC concentration showed that conversion was almost 100% with NiLG500 (pH = 9.4) catalyst and 100% and 96% with NiWB500 (pH = 8.8) catalyst, respectively. The XRD and TEM patterns of the two catalysts after 50 h gasification run showed higher sintering in NiLG500 (pH = 9.4) in which Ni particles were smaller in size.     

The growth mechanism of nickel in the preparation of Ni/Al2O3 catalysts studied by LEIS,XPS and catalytic activity

A series of Ni/Al₂O₃ catalysts prepared from vapor phase by the atomic layer epitaxy (ALE) technique have been studied. A model is proposed for the growth mechanism of nickel in its oxidic form on alumina, from sequences of treatments with Ni(acac)₂ and air. In the study activity measurements were combined with surface analysis by LEIS and XPS. During the first preparation sequence (< 5 wt% Ni) atomically dispersed nickel is obtained on the alumina support. The nickel atoms are catalytically inactive, but act as nuclei for the growth of the catalytically active Ni-species during the subsequent preparation sequences. The highest utilization of nickel atoms in the hydrogenation of toluene was obtained when the nickel nuclei were covered with one layer of active nickel species.     

Effects of Co dopants and flame conditions on the formation of Co/ZrO2 nanoparticles by flame spray pyrolysis and their catalytic properties in CO hydrogenation

The Co/ZrO₂ catalysts with various Co loadings (5–10 wt.%) were prepared by one-step flame spray pyrolysis (FSP) under different flame conditions. As revealed by XRD and TEM, all the resulting Co/ZrO₂ nanoparticles were composed of single-crystalline particles exhibiting the characteristic tetragonal structure of ZrO₂. Varying the amount of Co dopants during FSP synthesis did not alter the primary particle size of ZrO₂ which was determined to be ca. 14 nm. On the other hand, increasing precursor feed rate from 3 to 8 ml/min resulted in an increase of ZrO₂ crystallite size from 10 to 19 nm. The higher precursor feed rate produced higher enthalpy of flame and longer residence times, which increased coalescence and sintering of the particles. Compared to the Co/ZrO₂ prepared by conventional impregnation method, the catalytic activities of the FSP-made catalysts were much higher. Moreover, the hydrogenation rates of the FSP-made Co/ZrO₂ catalysts were increased with increasing Co loading and precursor feed rate. According to H₂ chemisorption and H₂ temperature program reduction results, the improvement of catalytic activity and C₂–C₆ selectivities of the FSP-made catalysts in the CO hydrogenation was attributed to the higher number of Co metal active sites and lower interaction between Co/CoO and ZrO₂ support obtained via the FSP synthesis.     

Determination of surface composition of alloy nanoparticles and relationships with catalytic activity in Pd–Cu/SiO2 cogelled xerogel catalysts

The combination of results from carbon monoxide chemisorption, X-ray diffraction, and transmission electron microscopy allowed calculating the surface composition of the palladium–copper nanoparticles in Pd–Cu/SiO₂ cogelled xerogel catalysts. Values obtained indicate a very pronounced surface enrichment with copper. Surface compositions obtained with this method, which combines three different experimental techniques, are in agreement with the literature data previously obtained for surface segregation in Pd–Cu/SiO₂ catalysts by other techniques as low energy ion scattering and X-ray photoelectron spectroscopy. While 1,2-dichloroethane hydrodechlorination over pure palladium mainly produces ethane, increasing copper content in bimetallic catalysts results in an increase in ethylene selectivity, to reach 100% in ethylene selectivity for the sample containing 1.4 wt.% of palladium and 3.0 wt.% of copper.