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十六烷基膦酸配合的复合氧化物纳米催化剂稳定的O/W乳液中甲苯单一氧化为苯甲醛(英文) 被引量:4
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作者 邓长顺 许孟霞 +7 位作者 董珍 李磊 杨金月 郭学峰 彭路明 薛念华 祝艳 丁维平 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2020年第2期341-349,共9页
苯甲醛是一种用途广泛的重要化学品,通过O2氧化甲苯制取苯甲醛是最佳生产途径,也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可,对该反应的多相催化过程也已经研究了几十年,但其性能仍远远低于... 苯甲醛是一种用途广泛的重要化学品,通过O2氧化甲苯制取苯甲醛是最佳生产途径,也是近几十年来工业界迫切需要的反应之一.虽然该反应在苄基上结合一个氧再脱除两个氢即可,对该反应的多相催化过程也已经研究了几十年,但其性能仍远远低于工业要求.当前的工业过程主要有甲苯氯化水解法和甲苯均相氧化法两种,但都存在严重的环境污染和腐蚀问题,且产品中含有少量卤素,阻碍了其在诸如香水或食品中的高端应用.近年来,以O2作为氧化剂及Pd,Au,Pt,Ag,Ru等贵金属或它们间的合金为催化剂的甲苯液相氧化反应研究取得了一些很好的进展,但仍然不能在高甲苯转化率下高选择性地得到苯甲醛.本课题组曾报道了一种高效的混相催化体系,以O2作为氧化剂将甲苯专一地催化氧化为苯甲醛,其中十六烷基膦酸-氧化铁(HDPA-FeOx)纳米颗粒处在甲苯和水的界面上,稳定了该O/W类皮克林乳液(Pickering).为了进一步提高催化剂晶格氧的移动性以提升催化活性,本文采用Mn, Co, Ni, Cu, Cr, Mo, V和Ti等一系列金属氧化物对催化剂HDPA-Fe Ox进行掺杂,同时使用一种特殊的纳米Al2O3作为载体,大大地增加了催化剂制备的便捷性和保证了催化剂在实际应用中的稳定性.TEM和XRD结果表明,Al2O3负载了金属氧化物后,其形貌仍为纳米棒状结构,并只能观察到Al2O3的晶相衍射峰,表明金属氧化物均匀地负载在其表面.BET结果表明,负载后的催化剂的孔结构与载体Al2O3类似.FT-IR结果表明,HDPA很好地吸附在了催化剂表面.TG结果表明,催化剂中HDPA含量与加入量相符,质量分数为~5%.结合前期工作可知,HDPA能够调整Fe M纳米棒表面催化性质,且以1 HDPA/nm2的密度为最佳,此时,甲苯液相氧化为苯甲醛的催化性能最佳.催化性能测试结果表明,催化剂吸附了HDPA后,甲苯的转化率显著增加,且只生成苯甲醛.在所考察的第二种掺杂金属中,以Ni的效果为最好.该催化剂在最佳反应条件下,甲苯转化率为83%(TOF=0.027nm–2·s–1),苯甲醛选择性为~100%.而Cr,Mo,V和Ti等高价金属则抑制了该反应,这也说明通过掺杂第二种金属调变晶格氧的活动性可影响反应性能.经过优化后,最佳反应条件为:p H值为2.5,反应温度为180°C.原位FT-IR结果表明, 180°C下,甲苯在吸附有HDPA的催化剂表面能够发生化学吸附,苄基C–H键解离并与晶格氧产生结合,形成了C6H5–CH2–O–Fe中间物种,该物种脱附即得苯甲醛.该温度下,表面HDPA对甲苯的化学吸附不可缺. 展开更多
关键词 甲苯氧化 苯甲醛 十六烷基膦酸 分子氧 皮克林
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Direct conversion of corn cob to formic and acetic acids over nano oxide catalysts 被引量:1
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作者 Liyuan Cheng Hong Liu +2 位作者 Yuming Cui nianhua xue Weiping Ding 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2014年第1期43-49,共7页
Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough... Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough accessible sites for cellulose, hemicellulose and monosaccharide from corn cob hydrolysis and oxidant. Chemical conversion of corn cob to organic acids is investigated over nano ceria, alumina, titania and zirconia under various atmospheres. Liquid products are mainly formic and acetic acids. A small amount of other compounds, such as D-xylose,D-glucose, arabinose and xylitol are also detected simultaneously. The yield of organic acids reaches 25%–29% over the nano oxide of ceria,zirconia and alumina with 3 h reaction time under 453 K and 1.2 MPa O2. The unique and fast conversion of corn cob is directly approached over the nano oxides. The results are comparative to those of biofermentation and offer an alternative method in chemically catalytic conversion of corn cob to useful chemicals in a one-pot chemical process. 展开更多
关键词 CORN COB chemical conversion NANO OXIDES BIOMASS formic ACID acetic ACID
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Adjacent acid sites cooperatively catalyze fructose to 5-hydroxymethylfurfural in a new, facile pathway 被引量:1
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作者 Xia Yu Yueying Chu +7 位作者 Lei Zhang Hui Shi Mingjiang Xie Luming Peng xuefeng Guo Wei Li nianhua xue Weiping Ding 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2020年第8期112-117,I0004,共7页
To study the effect of adjacent hydroxyl to the active sites, several acid catalysts, i.e. substituted benzoic acids with adjacent carboxyl are employed in the fructose dehydration to 5-hydroxymethylfurfural(HMF).Expe... To study the effect of adjacent hydroxyl to the active sites, several acid catalysts, i.e. substituted benzoic acids with adjacent carboxyl are employed in the fructose dehydration to 5-hydroxymethylfurfural(HMF).Experimental results reveal that Br?nsted acid sites with adjacent carboxyl present higher catalytic ability than isolated ones. Computational results suggest that the adjacent sites lead to co-interaction on fructose, corresponding more stable transition state and faster HMF formation rate. Based on the enhancement from the adjacent sites, a novel ordered mesoporous carbon(OMC) full of carboxyls in surface is prepared and turns out to be an effective solid catalyst for HMF production from fructose derived from biomass. 展开更多
关键词 Fructose dehydration Adjacent sites Cooperative catalysis 5-HYDROXYMETHYLFURFURAL
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Atomically Precise Water-Soluble Gold Nanoclusters:Synthesis and Biomedical Application
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作者 Qian Yan Zhaotong Yuan +8 位作者 Yating Wu Chunmei Zhou Yihu Dai Xiaoyue Wan Dan Yang Xu Liu nianhua xue Yan Zhu Yanhui Yang 《Precision Chemistry》 2023年第8期468-479,共12页
Atomically precise water-soluble gold nanoclusters(Au NCs)protected by organic ligands have attracted growing attention in serving as unique nanomaterials with the potential to generate theranostic tools(bioimaging,bi... Atomically precise water-soluble gold nanoclusters(Au NCs)protected by organic ligands have attracted growing attention in serving as unique nanomaterials with the potential to generate theranostic tools(bioimaging,biosensing,and biotherapy),due to their ultrasmall size,superior photoluminescence,good biocompatibility,and nontoxicity.More importantly,Au NCs afford a well-defined atomic packing structure and molecular purity,providing a superior platform to unravel the structure−performance correlations for biodistribution,biological pharmacokinetics,and excretion of Au NCs.In this Review,we mainly survey the synthesis of water-soluble Au NCs and the recent progress in biomedicine of Au NCs,including bioimaging,biosensing,and biotherapy.The effects of ligand and size on the biomedical properties are discussed in detail.We hope that the advances in this research area can expand the applications of Au NCs in biomedicine. 展开更多
关键词 Gold nanocluster well-defined structure WATER-SOLUBLE biodiagnostic THERANOSTIC
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