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81.
贵金属物种(Rh或Ir络合物)在均相羰基化和氢甲酰化催化过程得到了广泛的应用,但始终存在分离繁琐等问题,其均相多相化可很大程度上简化分离操作,故一直广受重视.单位点催化剂因其具有可与均相相比拟的较高金属利用率和选择性而成为均相多相化的重要研究方向之一.研究发现,在碘物种存在的情况下用于固载金属物种的配位键容易断裂,进而导致金属物种的流失,而通过离子键固载的[Rh(CO)2I2]–物种更加稳定,比如著名的甲醇羰基化“AceticaTM”工艺中,[Rh(CO)2I2]–负一价阴离子物种是以离子键的方式固定在带有阳离子骨架的甲基化聚乙烯吡啶树脂上.与甲醇羰基化过程类似的乙醇羰基化过程是生产重要化工中间体丙酸的主要途径之一,但该过程的均相多相化始终存在着稳定性差这一关键问题.为了解决这一问题,基于之前将固载于季鏻盐聚合物的[Rh(CO)I3]2–应用于甲醇羰基化的工作,我们将类似的季鏻盐聚合物固载Rh基催化剂Rh-TPISP用于多相乙醇羰基化过程,通过多种表征进一步证明了Rh物种和P物种结构,并提出了“双离子键”模型.P的K边XANES证明了聚合物TPISP的季鏻化阳离子骨架特征.HAADF-STEM测试表明Rh-TPISP中的Rh呈现单位点分散的状态.Rh的XPS和XANES结果证明了Rh-TPISP中Rh物种的价态介于0~+1.通过EXAFS的拟合解析给出了[Rh(CO)I3]2–活性中心结构.由于[Rh(CO)2I2]–为经典的羰基化活性中心,为了进一步证明该结构的正确性,我们将Rh-TPISP的EXAFS和IR谱图与标样[PPh3Et]+[Rh(CO)2I2]–对比发现:在EXAFS谱图中,Rh-TPISP中的Rh-C峰高低于[PPh3Et]+[Rh(CO)2I2]–的Rh-C峰高,而Rh-TPISP中的Rh-I峰高高于[PPh3Et]+[Rh(CO)2I2]–的Rh-I峰高,这就说明Rh-TPISP中Rh物种的Rh-C配位数小于2,而Rh-I配位数大于2;在IR谱图中,标样[PPh3Et]+[Rh(CO)2I2]–中有两个羰基振动峰,与该物种的两个Rh-C配位键相符,而Rh-TPISP中的只有一个羰基振动峰,说明Rh-C配位数为1.因此,Rh-TPISP催化剂的季鏻盐骨架中的每个P物种带有一个正电荷,每个带有两个负电荷的[Rh(CO)I3]2–通过与两个[P]+的静电作用进行固载,形成“双离子键”结构.该催化剂在固定床乙醇羰基化过程中表现出优异的羰基化活性、选择性和稳定性.在3.5 MPa、195 oC反应近1000 h后,Rh-TPISP催化剂TOF保持在约350 h–1,丙酰基选择性为95%以上,高出所有文献报道的均相和多相乙醇羰基化活性.其较高的活性主要是因为[Rh(CO)I3]2–比传统Rh活性相[Rh(CO)2I2]–具有更强的富电子性,而较高的稳定性主要是由于“双离子键”这种强静电作用比“AceticaTM”工艺中“单离子键”更有利于Rh物种的固载.故Rh-TPISP催化剂中的“双离子键”对其优异的催化性能具有极其重要的作用,对后续多相乙醇羰基化的发展具有重要意义. 相似文献
82.
Electrochemical Synthesis of Tetrahexahedral Rhodium Nanocrystals with Extraordinarily High Surface Energy and High Electrocatalytic Activity 下载免费PDF全文
Neng‐Fei Yu Dr. Na Tian Dr. Zhi‐You Zhou Long Huang Jing Xiao Yu‐Hua Wen Prof. Shi‐Gang Sun 《Angewandte Chemie (International ed. in English)》2014,53(20):5097-5101
Noble metal nanocrystals (NCs) enclosed with high‐index facets hold a high catalytic activity thanks to the high density of low‐coordinated step atoms that they exposed on their surface. Shape‐control synthesis of the metal NCs with high‐index facets presents a big challenge owing to the high surface energy of the NCs, and the shape control for metal Rh is even more difficult because of its extraordinarily high surface energy in comparison with Pt, Pd, and Au. The successful synthesis is presented of tetrahexahedral Rh NCs (THH Rh NCs) enclosed by {830} high‐index facets through the dynamic oxygen adsorption/desorption mediated by square‐wave potential. The results demonstrate that the THH Rh NCs exhibit greatly enhanced catalytic activity over commercial Rh black catalyst for the electrooxidation of ethanol and CO. 相似文献
83.
Catalytic Ethanolysis of Kraft Lignin into High‐Value Small‐Molecular Chemicals over a Nanostructured α‐Molybdenum Carbide Catalyst 下载免费PDF全文
Rui Ma Wenyue Hao Xiaolei Ma Ye Tian Prof. Yongdan Li 《Angewandte Chemie (International ed. in English)》2014,53(28):7310-7315
We report the complete ethanolysis of Kraft lignin over an α‐MoC1?x/AC catalyst in pure ethanol at 280 °C to give high‐value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C6–C10 esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg?1. C6 alcohols and C8 esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700–1400, differing in steps of 58 units, which is the weight of the branched‐chain linkage C3H6O in lignin. Hydrogen was found to have a negative effect on the formation of the low‐molecular‐weight products. 相似文献
84.
This study aims at contributing to quinine extraction using supercritical CO2 and ethanol as a co-solvent. The diffusion coefficients of quinine in supercritical CO2 are measured using the Taylor dispersion technique when quinine is pre-dissolved in ethanol. First, the diffusion coefficients of pure ethanol in the supercritical state of CO2 were investigated in order to get a basis for seeing a relative change in the diffusion coefficient with the addition of quinine. We report measurements of the diffusion coefficients of ethanol in scCO2 in the temperature range from 304.3 to 343 K and pressures of 9.5, 10 and 12 MPa. Next, the diffusion coefficients of different amounts of quinine dissolved in ethanol and injected into supercritical CO2 were measured in the same range of temperatures at p = 12 Mpa. At the pressure p = 9.5 MPa, which is close to the critical pressure, the diffusion coefficients were measured at the temperature, T = 343 K, far from the critical value. It was found that the diffusion coefficients are significantly dependent on the amount of quinine in a small range of its content, less than 0.1%. It is quite likely that this behavior is associated with a change in the spatial structure, that is, the formation of clusters or compounds, and a subsequent increase in the molecular weight of the diffusive substance. 相似文献
85.
Dr. Hongjing Wang Shiqian Jiao Songliang Liu Hugang Zhang Dr. You Xu Prof. Xiaonian Li Dr. Ziqiang Wang Prof. Liang Wang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(58):14472-14477
The optimization of structure and composition is essential to improve the performance of catalysts. Herein, mesoporous nanoparticles assembled PdNi/Ni nanotubes (mPdNi/Ni NTs) are successfully fabricated using nickel nanowires as sacrificial template. The combination of nanotubular structure with mesoporous nanoparticle morphology can provide facilitated transfer channels and sufficient active sites, allowing the full contact and reaction between catalysts and reactants. Therefore, the synthesized mPdNi/Ni NTs exhibite superior ethanol oxidation performance to mesoporous Pd nanotubes and commercial Pd black. This study proposes a rational strategy for the development of nanoparticle assembled nanotubes with surface mesoporous morphology, which can greatly improve catalytic performance in various electrocatalytic fields. 相似文献
86.
Yongkang Quan Prof. Guorong Wang Dujuan Li Prof. Zhiliang Jin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(66):16448-16460
At present, inefficient charge separation of single photocatalyst impedes the development of photocatalytic hydrogen evolution. In this work, the CoSX/NiCo-LDH core-shell co-catalyst was cleverly designed, which exhibit high activity and high stability of hydrogen evolution in anhydrous ethanol system when coupled with CdS. Under visible light (λ≥420 nm) irradiation, the 3 %Co/NiCo/CdS composite photocatalyst exhibits a surprisingly high photocatalytic hydrogen evolution rate of 20.67 mmol g−1 h−1, which is 59 times than that of the original CdS. Continuous light for 20 h still showed good cycle stability. In addition, the 3 %Co/NiCo/CdS composite catalyst also shows good hydrogen evolution performance under the Na2S/Na2SO3 and lactic acid system. The fluorescence (PL), ultraviolet-visible diffuse reflectance (UV-vis) and photoelectrochemical tests show that the coupling of CdS and CoSX/NiCo-LDH not only accelerates the effective transfer of charges, but also greatly increases the absorption range of CdS to visible light. Therefore, the hydrogen evolution activity of the composite photocatalyst has been significantly improved. This work will provide new insights for the construction of new co-catalysts and the development of composite catalysts for hydrogen evolution in multiple systems. 相似文献
87.
Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability 下载免费PDF全文
Dr. Yunteng Qu Dr. Yunzhi Gao Dr. Long Wang Dr. Jiancun Rao Dr. Geping Yin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):193-198
We have designed a new Pt/SnO2/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO2 structure. The Sn2+ cations reduce graphene oxide (GO), leading to the in situ formation of SnO2/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO2 NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO2/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO2 NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems. 相似文献
88.
The catalytic role of various inert solid supports on acceleration of alcohol fermentation by Saccharomyces cerevisiae was investigated. The enhanced rate of alcohol production was dependent on the nature of the support as well as on the amount
used. Among all the tested supports, chitosan flakes showed the maximum yield of alcohol (93% of theoretical yield). This
higher rate of alcohol production was associated with the twofold increase in the activity of alcohol dehydrogenase over control.
Our results suggest that the addition of a small fraction of solids in submerged fermentations to facilitate cell anchorage
for enhanced metabolic activity is easier and more economical compared to cell immobilization processes.
IICT Communication No. 4266. Some of the results in this article are covered under a patent. 相似文献
89.
A.P. Farkas 《Surface science》2007,601(1):193-200
The adsorption, desorption and dissociation of ethanol have been investigated by work function, thermal desorption (TPD) and high resolution electron energy loss (HREELS) spectroscopic measurements on Mo2C/Mo(1 0 0). Adsorption of ethanol on this sample at 100 K led to a work function decrease suggesting that the adsorbed layer has a positive outward dipole moment By means of TPD we distinguished three adsorption states, condensed layer with a Tp = 162 K, chemisorbed ethanol with Tp = 346 K and irreversibly bonded species which decomposes to different compounds. These are hydrogen, acetaldehyde, methane, ethylene and CO. From the comparison of the Tp values with those obtained following their adsorption on Mo2C it was inferred that the desorption of methane and ethylene is reaction limited, while that of hydrogen is desorption limited process. HREEL spectra obtained at 100 K indicated that at lower exposure ethanol undergoes dissociation to give ethoxy species, whereas at high exposure molecularly adsorbed ethanol also exists on the surface. Analysis of the spectral changes in HREELS observed for annealed surface assisted to ascertain the reaction pathways of the decomposition of adsorbed ethanol. 相似文献
90.
Effects of P content in a P/HZSM-5 catalyst on the conversion of ethanol to hydrocarbons 总被引:1,自引:0,他引:1
A series of P/HZSM-5 catalysts prepared by impregnation method were used for ethanol conversion to lower olefins. The catalysts were characterized by X-ray diffraction (XRD), NH3-temperature-programmed desorption (NH3-TPD) and N2 adsorption-desorption measurements. It was found that the P/HZSM-5 catalysts showed high activity and selectivity toward light olefins. The selectivities of propylene and butylene can be improved with the introduction of phosphorus (P). When the content of P reached 3.0 wt%, more than 18.9% propylene in the gaseous products was obtained over the P/HZSM-5 catalyst at 450 ?C. The introduction of P modified the strong Br?nsted acid sites of the original HZSM-5 catalysts and P/HZSM-5 catalysts could resist coke formation and showed good stability. 相似文献