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Zn-Zr-Al氧化物催化乙醇合成碳酸二乙酯(英文) 被引量:6
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作者 张健 阎婷婷 +3 位作者 杨宇森 孙嘉略 林彦军 卫敏 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2019年第4期515-522,M0002,共9页
乙醇作为一种重要的可再生平台化学品,其高值转化已引起研究者的广泛关注.碳酸二乙酯(DEC)是乙醇转化的重要衍生物,作为合成中间体、绿色溶剂和燃油添加剂,具有低毒、无污染的优点.目前,以乙醇为底物合成DEC主要有以下方法:光气法、氧... 乙醇作为一种重要的可再生平台化学品,其高值转化已引起研究者的广泛关注.碳酸二乙酯(DEC)是乙醇转化的重要衍生物,作为合成中间体、绿色溶剂和燃油添加剂,具有低毒、无污染的优点.目前,以乙醇为底物合成DEC主要有以下方法:光气法、氧化羰基化法、酯交换法和尿素醇解法.其中,尿素醇解法因成本低、操作简便、产物易分离等优点而备受关注,包括两个连续过程:乙醇和尿素反应生成中间体氨基甲酸乙酯(EC), EC与乙醇进一步反应生成DEC.本文采用水滑石(Zn_2Zr_xAl-LDH)为前体,经结构拓扑转变制备了一系列酸碱双功能金属氧化物催化剂(Zn_2Zr_xAl-MMO),用于催化乙醇合成DEC.通过改变LDHs前体元素比例调控氧化物的酸碱性质和催化性能,最优催化剂Zn_2Zr_(0.1)Al-MMO对产物DEC产率达到42.1%,为目前报道的金属氧化物催化剂的最高产率.CO_2-TPD和NH_3-TPD结果表明,随着Zr含量的增加,催化剂的总碱性位点(BTOTAL)和总酸性位点(ATOTAL)浓度呈现先增加后减少的趋势,其中以Zn_2Zr_(0.1)Al-MMO样品最大,表明Zr对调节Zn_2Zr_xAl-MMO催化剂酸碱性质起到了关键作用.研究发现, Zn_2Zr_(0.1)Al-MMO催化剂样品具有最大浓度的中强碱位点(BM)和弱酸位点(AW).为了揭示构效关系,进一步研究了DEC产率与催化剂酸碱位点浓度的函数关系.结果表明, DEC产率与中强碱位点(BM)或弱酸位点(AW)的浓度呈现正相关性;而且中强碱位点和弱酸位点之间的协同作用对提升催化性能有重要贡献.与目标催化剂相比,对照样品Zn_2Al-MMO表现出较高的EC产率(54.7%)和较低的DEC产率(28.3%),表明目标催化剂中的ZrO_2组分能够有效活化中间产物EC,促使其进一步转化为DEC.此外, ZrO_2和Al_2O_3均显示出较高的EC产率(68.0%和81.2%),但DEC产率(8.7%和5.3%)较低,说明目标催化剂中的ZnO组分能有效活化乙醇分子,消耗生成的中间体EC.原位红外结果证实, ZrO_2提供的弱酸性位点促进了尿素和中间产物EC的活化吸附,在2207 cm^(-1)处观察到nN(28)C(28)O特征吸附峰;而乙醇在中强碱性位点(Zn_2(10)-O^(2-))活化,在2973, 2925, 2900,1078和1052 cm^(-1)处观察到乙醇的特征吸收峰.此外, Zn_2Zr_(0.1)Al-MMO催化剂表现出良好的稳定性和可重复使用性,循环使用5次后, DEC产率损失低于5%. 展开更多
关键词 水滑石 金属氧化物 酸碱催化反应 乙醇转化
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几何效应促进水滑石催化剂实现对羟醛缩合反应性能提升 被引量:4
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作者 王慧敏 邴威瀚 +8 位作者 陈春源 杨宇森 徐明 陈利芳 郑雷 李晓林 张欣 殷建军 卫敏 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2020年第8期1279-1287,共9页
近年来,绿色发展观念深入人心.与液体碱相比,固体碱催化剂由于其环境友好、腐蚀性小、易于回收等优点引起了科研工作者的广泛关注.但是,在固体碱催化领域,如何对碱性位点进行调控从而使羟醛缩合反应获得优异性能仍然是一个很大挑战.甲... 近年来,绿色发展观念深入人心.与液体碱相比,固体碱催化剂由于其环境友好、腐蚀性小、易于回收等优点引起了科研工作者的广泛关注.但是,在固体碱催化领域,如何对碱性位点进行调控从而使羟醛缩合反应获得优异性能仍然是一个很大挑战.甲醛和异丁醛反应生成的产物羟基新戊醛是精细化工合成中一类非常重要的有机中间体,广泛应用于药物、润滑油、聚酯树脂等化工产品生产.目前,应用于该反应的固体碱催化剂催化活性较低,性能有待进一步提升.因此,设计一类结构可调、性能优异的固体碱催化剂材料迫在眉睫.本文利用水滑石材料结构特有的记忆效应制备了一系列掺杂镓、铟的钙铝水滑石催化剂,并将其应用于甲醛与异丁醛缩合生成羟基新戊醛反应,并探讨了不同离子半径的元素掺杂对钙铝水滑石结构产生的影响和作用.结果表明,复原后的re-Ca4Al0.90Ga0.10-LDH对羟基新戊醛的生成表现出优异的性能(HPA产率为72%),达到固体碱催化剂催化该反应的最高水平,甚至与液体碱催化剂水平相当.通过氘代氯仿原位红外光谱对催化剂的活性位点进行表征,结果证明掺入镓之后使弱碱性位点的相对浓度增加,而掺入铟后使弱碱性位点的相对浓度减小.进而将弱碱性位点的数量和中强碱性位点的数量与催化性能结果进行构效关联,证明了该反应中的活性中心为弱碱性位点(7配位Ca-OH).该弱碱性位点不仅促进了产物羟基新戊醛的脱附,还提高了反应的活性和选择性,使得羟基新戊醛的产率大大提升.通过EXAFS手段对催化剂的精细结构进行表征,证明了掺入镓和铟后,钙铝水滑石晶格发生了膨胀,Ca-O键长增加.其中,掺杂铟元素使得铟与水滑石层间羟基形成额外的In-OH化学键,从而使七配位的Ca-OH位点浓度降低.通过XPS和DFT计算证明了掺入镓和铟后催化剂的碱性强度没有发生变化,说明镓和铟的掺入只改变了碱性位点数量而对碱性位点强度没有明显影响.最后,对催化剂结构和性能进行了关联,证明了镓作为结构助剂掺入到水滑石层板中产生的几何效应使得晶格发生膨胀从而暴露了更多的活性位点,实现了催化反应活性的极大提升.该工作揭示了不同离子半径元素的掺杂所产生的几何效应对催化活性位点的有效调控作用,从而大大提升了羟醛缩合反应性能,为制备新型优异的固体碱催化剂提供了思路和依据. 展开更多
关键词 固体碱催化剂 几何结构 结构助剂 羟醛缩合 复原水滑石
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Regulation of phenylpropanoid biosynthesis by MdMYB88 and MdMYB124 contributes to pathogen and drought resistance in apple 被引量:5
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作者 Dali Geng Xiaoxia Shen +8 位作者 Yinpeng Xie yusen yang Ruiling Bian Yuqi Gao Pengmin Li Liying Sun Hao Feng Fengwang Ma Qingmei Guan 《Horticulture Research》 SCIE 2020年第1期1525-1535,共11页
MdMYB88 and MdMYB124 have been demonstrated to be responsible for lignin accumulation in apple under drought stress.In this study,using a metabolomic approach,we identified differentially accumulated phenylpropanoid a... MdMYB88 and MdMYB124 have been demonstrated to be responsible for lignin accumulation in apple under drought stress.In this study,using a metabolomic approach,we identified differentially accumulated phenylpropanoid and flavonoid metabolites in MdMYB88/124 transgenic RNAi plants under control and long-term drought stress conditions in apple roots.We confirmed the regulation of phenylalanine by MdMYB88 and MdMYB124 via UPLC-MS in apple roots under both control and drought conditions.Using Electrophoretic Mobility Shift Assay(EMSA)and ChIPquantitative PCR(qPCR)analyses,we found that MdMYB88 positively regulates the MdCM2 gene,which is responsible for phenylalanine biosynthesis,through binding to its promoter region.Under long-term drought conditions,MdMYB88/124 RNAi plants consistently accumulated increased amounts of H2O2 and MDA,while MdMYB88 and MdMYB124 overexpression plants accumulated decreased amounts of H2O2 and MDA.We also examined the accumulation of metabolites in the phenylpropanoid biosynthesis pathway in the leaves of MdMYB88 and MdMYB124 transgenic apple plants after long-term drought stress.We found that metabolites responsible for plant defense,including phenylpropanoids and flavonoids,accumulated less in the RNAi plants but more in the overexpression plants under both control and drought conditions.We further demonstrated that MdMYB88/124 RNAi plants were more sensitive to Alternaria alternata f.sp.mali and Valsa mali,two pathogens that currently severely threaten apple production.In contrast,MdMYB88 and MdMYB124 overexpression plants were more tolerant to these pathogens.The cumulative results of this study provided evidence for secondary metabolite regulation by MdMYB88 and MdMYB124,further explained the molecular roles of MdMYB88 and MdMYB124 in drought resistance,and provided information concerning molecular aspects of their roles in disease resistance. 展开更多
关键词 DROUGHT resistance ROOTS
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Structural Domain Imaging and Direct Determination of Crystallographic Orientation in Noncentrosymmetric Ca3 Ru2O7 Using Polarized Light Reflectance
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作者 唐国雄 文理斌 +12 位作者 邢晖 刘文杰 彭劲 王瑜 李宇鹏 吕柏江 杨宇森 姚超 吴越珅 孙弘 许祝安 毛志强 刘荧 《Chinese Physics Letters》 SCIE CAS CSCD 2020年第10期43-47,共5页
The noncentrosymmetricity of a prototypical correlated electron system Ca3Ru2O7 renders extensive interest in the possible polar metallic state,along with multiple other closely competing interactions.However,the stru... The noncentrosymmetricity of a prototypical correlated electron system Ca3Ru2O7 renders extensive interest in the possible polar metallic state,along with multiple other closely competing interactions.However,the structural domain formation in this material often complicates the study of intrinsic material properties.It is crucial to fully characterize the structural domains for unrevealing underlying physics.Here,we report the domain imaging on Ca3Ru2O7 crystal using the reflection of polarized light at normal incidence.The reflection anisotropy measurement utilizes the relative orientation between electric field component of the incident polarized light and the principal axis of the crystal,and gives rise to a peculiar contrast.The domain walls are found to be the interfaces between 90° rotated twin crystals by complementary magnetization measurements.A distinct contrast in reflectance is also found in the opposite cleavage surfaces,owing to the polar mode of the RuO6 octahedra.More importantly,the analysis of the contrast between all inequivalent cleavage surfaces enables a direct determination of the crystallographic orientation of each domain.Such an approach provides an efficient yet feasible method for structural domain characterization,which can also find applications in noncentrosymmetric crystals in general. 展开更多
关键词 SYMMETRIC CLEAVAGE utilize
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不饱和醛选择性加氢高效催化剂的研究
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作者 杨星月 周石杰 +1 位作者 杨宇森 卫敏 《化学进展》 SCIE CAS CSCD 北大核心 2024年第3期297-318,共22页
不饱和醛的选择性加氢作为一类重要的精细化学品加工转化过程,在香精香料、药物食品生产、农产品加工等领域具有广泛应用。但是目前所应用催化剂的反应活性仍有待提高,需对催化剂进行进一步调控。本文总结了提高催化剂加氢选择性的三种... 不饱和醛的选择性加氢作为一类重要的精细化学品加工转化过程,在香精香料、药物食品生产、农产品加工等领域具有广泛应用。但是目前所应用催化剂的反应活性仍有待提高,需对催化剂进行进一步调控。本文总结了提高催化剂加氢选择性的三种策略,包括:改变金属活性位点的电子性质、增强金属活性位点与亲电位点之间的协同作用和利用结构效应来改变催化剂对于C=O键或C=C键的吸附能力和加氢活性。概括了氢源种类、反应溶剂、反应温度和氢气压力等反应条件对催化性能的影响。并归纳了不饱和醛选择性加氢有关的密度泛函理论计算、反应的动力学模型及反应中的构效关系。最后,讨论了不饱和醛选择性加氢催化剂面临的问题和挑战,并提出了可行的解决方案。 展开更多
关键词 选择性加氢 不饱和醛 动力学研究 构效关系 结构设计
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Glycerol aerobic oxidation to glyceric acid over Pt/hydrotalcite catalysts at room temperature 被引量:8
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作者 Junbo Zhang Xiaolin Li +7 位作者 Ming Xu yusen yang Yinwen Li Ning Liu Xiaoyu Meng Lifang Chen Shuxian Shi Min Wei 《Science Bulletin》 SCIE EI CAS CSCD 2019年第23期1764-1772,共9页
Glycerol(GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals(mainly Au, Pd, Pt) are most commonly employ... Glycerol(GLY) aerobic oxidation in an aqueous solution is one of the most prospective pathways in biomass transformation, where the supported catalysts based on noble metals(mainly Au, Pd, Pt) are most commonly employed. Herein, Pt nanoparticles supported on rehydrated MgxAl1-hydrotalcite(denoted as re-MgxAl1-LDH-Pt) were prepared via impregnation-reduction method followed by an in situ rehydration process, which showed high activity and selectivity towards GLY oxidation to produce glyceric acid(GLYA) at room temperature. The metal-support interfacial structure and catalyst basicity were modulated by changing the Mg/Al molar ratio of the hydrotalcite precursor, and the optimal performance was achieved on re-Mg6Al1-LDH-Pt with a GLY conversion of 87.6% and a GLYA yield of 58.6%, which exceeded the traditional activated carbon and oxide supports. A combinative study on structural characterizations(XANES, CO-FTIR spectra, and benzoic acid titration) proves that a higher Mg/Al molar ratio promotes the formation of positively charged Ptd+species at metal-support interface, which accelerates bond cleavage of a-C–H and improves catalytic activity. Moreover, a higher Mg/Al molar ratio provides a stronger basicity of support that contributes to the oxidation of terminal-hydroxyl and thus enhances the selectivity of GLYA. This catalyst with tunable metal-support interaction shows prospective applications toward transformation of biomass-based polyols. 展开更多
关键词 Rehydrated hydrotalcites Interfacial structure Support basicity Active sites Rate-determining step
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