Essential Quality Attributes of Tangible Bio‐Oils from Catalytic Pyrolysis of Lignocellulosic Biomass

This review covers the characteristics of pyrolysis and catalytic pyrolysis bio‐oils by focusing on the fundamental factors that determine bio‐oil upgradability. The abundant works on the subject of bio‐oil production from lignocellulosic biomass were studied to establish the essential attributes of the bio‐oils for assessment of the oil stability and upgradability. Bio‐oils from catalytic pyrolysis processes relating to catalysts of different compositions and structures are discussed. A general relationship between the higher heating value and the oxygen content in the catalytic pyrolysis oils exists, but this relationship does not apply to the thermal pyrolysis oil. Reporting bio‐oil yield is meaningful only when the oxygen content of the oil is measured because the pyrolytic oil stability is mainly determined by the oxygen content. Isoenergy plot that associates bio‐oil yield with oxygen content is presented and discussed.     

离子液体溶胀对煤直接液化残渣结构及热解性能的影响

采用四种相同阴离子不同有机链长阳离子的离子液体([EMIM][MeSO_4]、[BMIM][MeSO_4]、[HMIM][MeSO_4]和[OMIM][MeSO_4])对煤直接液化残渣(DCLR)进行溶胀处理,通过SEM、FT-IR和TG-DTG表征,分析了各离子液体溶胀对煤直接液化残渣溶胀效果、表面形貌、官能团分布、主体结构和热解性能的影响。溶胀结果表明,不同链长离子液体对煤直接液化残渣具有不同的溶胀效果,[HMIM][MeSO_4]对残渣溶胀效果最好,其溶胀度高达1.78。FT-IR表明,不同链长离子液体会不同程度地破坏煤中C-H键,使得脂肪族和芳香族类化合物的相对含量有所差异。由TG-DTG可知,不同链长离子液体溶胀对残渣热解性能的影响具有较大差异,其中,以离子液体[OMIM][MeSO_4]溶胀对残渣的热解最为有利,失重率高达47.5%;而离子液体[BMIM][MeSO_4]溶胀在一定程度上抑制了残渣的热解,其失重率低于未经溶胀处理的残渣。基于Coats-Redfern法的热解动力学分析表明,煤直接液化残渣及其溶胀残渣在低温段(180-480℃)的热解过程均符合二级反应动力学,高温段(480-825℃)均以三级和四级反应动力学为宜。另外,不同链长离子液体溶胀处理明显改变了残渣的热解活化能,其链越长残渣的热解活化能越高。     

Valorization of Oceanic Waste Biomass: A Catalytic Perspective

Efficacious waste utilization is vital in context of sustainability. The past decade has witnessed attempts of usage of land biomass and wastes for various applications, contributing towards a sustainable society. Exploitation of the marine biomass, which does not compete with habitation and food production like land biomass has been largely unnoticed and therefore not being utilized judiciously. Researchers have mainly exploited these resources as functional materials having significant potential applications. However, a catalytic perspective for the valorisation of these polymers arising from oceanic waste widens their scope and ameliorates its use. The objective of the present review is to demonstrate the effectiveness of chitin/chitosan as a catalyst and as a feedstock for deriving important fuels and chemicals. It displays all the reactions heterogeneously catalyzed by them along with the strategic methodology. Their important catalytic organic transformations attempted so far, have also been discussed. The future perspectives are also presented which if inculcated would improve the value addition of the waste, paving a way for greener and imperishable world.     

开关型Pickering乳液体系

Pickering乳液以胶体尺寸的固体粒子代替传统表面活性剂作为稳定剂,具有超稳定,生物相容性好以及对环境友好等优点。开关型Pickering乳液可随pH值、CO₂/N₂浓度、温度、磁场强度及光强度等条件的变化而改变固体乳化剂的表面润湿性,实现在“乳化”与“破乳”之间的快速转换,在非均相催化、乳液聚合等诸多领域有广泛的应用前景。本文全面总结了近年来开关型Pickering乳液的研究进展及其在界面催化系统、液膜处理有机废水、药物的包封与释放等方面的应用。     

单气室固体氧化物燃料电池的材料、微堆结构与相关应用

单气室固体氧化物燃料电池（SC-SOFC）是一种整个电池处在单一气室中,阳极和阴极分别对混合气体中的燃料和氧气进行选择催化产生电动势的特殊结构燃料电池. SC-SOFC因其独特的原理和结构而具有无需密封、易于堆叠、可以快速启动和不易发生积碳等诸多优点,有很大的应用潜力. 作者在SC-SOFC的原理和特点的基础上,系统地总结了SC-SOFC所用材料、微堆结构设计、衰退机制及应用方面的研究进展;以提高SC-SOFC微堆的输出电压和功率为目的,改进预混气体环境下运行的微堆结构,采取星型布局的四电池微堆其输出功率提高到420 mW;随后,逐步改进供气方式,结合计算流体力学数值模拟研究,提出了单路多点供气和双路多点供气模式,成功地将单个SC-SOFC微堆模块的输出功率提升到8.178 W,进而开展了微堆模块外部串并联和与燃烧器的结合实验验证. 研究结果表明,SC-SOFC可以很便捷地连接成微堆模块并产生数瓦的输出功率,未来有望用于以供热为主型的热电联供系统. 作者还借助原位电阻和开路电压的原位同步测试,阐明了Ni在CH₄-O₂气氛中的反复氧化-还原循环是SC-SOFC发生不可逆衰退的主要机制,这一发现后来催生出氧化-还原法制备多孔金属的新技术.     

High effects of smoke suppression and char formation of Ni?Mo/Mg(OH)2 for polypropylene

The Ni? Mo/Mg(OH)₂ (NMM) hybrid as an efficient flame retardancy and smoke suppression composite for polypropylene (PP) was synthesized through Ni? Mo co‐precipitation on the surface of Mg(OH)₂ (MH) hexagonal nanosheets. Compared to PP/MH, PP/NMM exhibited excellent smoke suppressing and flame retardancy on the heat release rate, total heat release, smoke production rate, total smoke production, CO production rate and total CO production with the same loading. The reduced hazard of PP/NMM was mainly attributed to the high physical barrier effect of compact char residues on heat, smoke and combustible gas. The mechanism study indicated that multiwalled carbon nanotubes (MWCNTs) generated from the catalytic carbonization of PP by the Ni? Mo compound could play the role of “rebar” to strengthen the char residues, avoid the generation of cracks and form highly compact char layer. Furthermore, MgO could facilitate the production of MWCNTs through changing the pyrolysis process of PP and increasing the reaction time between pyrolysis gas and Ni? Mo compound. Hence, the new Ni? Mo/MH catalyst hybrid may explore the potential for solving the tough problem of the flammability and heavy smoke of the polyolefins system.     

Nb(iPrNPMe2)3Fe–PMe3: A potential high reactivity heterobimetallic catalyst for acetylene cycloadditions

Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(ⁱPrNPMe₂)₃Fe–PMe₃, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(ⁱPrNPMe₂)₃Fe–PMe₃ can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(ⁱPrNPMe₂)₃Fe–PMe₃ to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(ⁱPrNPMe₂)₃Fe–PMe₃ is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(ⁱPrNPMe₂)₃Fe–PMe₃ moves from niobium to iron.     

Pt/CeL重整催化剂的制备及其石脑油芳构化性能

为克服常规氧化铝重整催化剂氯离子流失及其对设备的腐蚀等问题,通过离子交换法制备了Ce~(3+)改性的L分子筛,采用浸渍法制备了Pt/CeL重整催化剂;用XRD、N_2吸附-脱附、NH_3-TPD和Py-FTIR等手段对载体和催化剂进行了表征,并以硫含量为0.50μg/mL的工业精制石脑油为原料,在固定床微型反应装置上评价了Pt/CeL催化剂的重整芳构化性能。结果表明,Ce~(3+)离子交换可提高载体的酸量和酸强度,而不会破坏L分子筛的骨架结构;Ce~(3+)改性后的Pt/CeL催化剂其重整芳构化性能明显提高,活性与选择性达到氧化铝型商业重整催化剂的水平,说明适当的酸性对重整催化剂芳构化反应有显著的促进作用。     

Characterization of new Pt(IV)–thiazole complexes: Analytical,spectral, molecular modeling and molecular docking studies and applications in two opposing pathways

New thiazole derivatives were synthesized and fully characterized, then coordinated with PtCl₄ salt. Also, the newly synthesized Pt(IV) complexes were investigated analytically (elemental and thermogravimetric analyses), spectrally (infrared, UV–visible, mass, ¹H NMR, ¹³C NMR, X‐ray diffraction) as well as theoretically (kinetics, modeling and docking). The data extracted led to the establishment of the best chemical and structural forms. Octahedral geometry was the only formula proposed for all complexes, which is favorable for d⁶ systems. The molecular ion peaks from mass spectral analysis coincide with all analytical data, confirming the molecular formula proposed. X‐ray diffraction (XRD) and scanning electron microscopy (SEM) allowed discrimination of features between crystalline particles and other amorphous morphology. By applying Gaussian09 as well as HyperChem 8.2 programs, the best structural forms were obtained, as well as computed significant parameters. Computed parameters such as softness, hardness, surface area and reactivity led us towards application in two opposing pathways: tumor inhibition and oxidation activation. The catalytic oxidation for CO was conducted over PtO₂, which was yielded from calcination of the most reactive complex. The success of catalytic role for synthesized PtO₂ was due to its particulate size and surface morphology, which were estimated from XRD patterns and SEM images, respectively. The antitumor activity was tested versus HCT‐116 and HepG‐2 cell lines. Mild toxicity was recorded for two of the derivatives and their corresponding complexes. This degree of toxicity is more favorable in most cases, due to exclusion of serious side effects, which is coherently attached with known antitumor drugs.     

简易振动台试验设备研制

为了完成多桩型复合地基抗液化性能振动台试验,利用实验室已有的反力墙和作动器,设计了一个小型的简易单向振动台系统和堆叠式剪切模型箱。堆叠式剪切模型箱内部尺寸为1200mm×800mm×772mm,由8层铝合金框架和7层橡胶条叠合而成。利用ANSYS有限元软件对模型箱及地基-模型箱进行了动力分析,并通过饱和粉细砂地基模型振动台试验验证了模型箱的效果。结果表明,所设计的模型箱能够较成功地模拟天然场地的边界条件,为多桩型复合地基抗液化性能振动台试验的顺利进行打下基础。