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Controllable Cyclopalladated Polythiophene Imine Monolayer by Self-Assembly, Hybrid Doping and Electrochemical Polymerization: A Simple Way to Enhance Activity and Stability 自组装、杂化掺杂和电化学聚合的可控环钯化聚噻吩亚胺单分子膜:一种提高活性和稳定性的简单方法
Pub Date : 2021-12-13 DOI: 10.21926/cr.2201003
Louguangshu Huang, Hui Liu, Xiaoxia Xue, Wuduo Zhao, Tiesheng Li
In this article, an approach to generate self-assembly cyclopalladated polythiophene imine monolayers (denoted as ITO@Pd-CPTIMs) is described. The monolayers were fabricated by combining self-assembly (SA), hybrid doping (HD), and electrochemical polymerization (ECP) called SA-HD-ECP. The catalytic activity and stability of the polymerized monolayers in the Suzuki coupling reaction were improved by modulating the structure and morphology in hybrid doping using different thiophene derivatives, concentrations, and scanning numbers during electrochemical polymerization. Morphological changes in the catalytic surface associated with catalytic activity were investigated. ITO@Pd-PTF could improve catalytic activity with a higher TON value (45000 mol/molcat) and attain recycling ability at least 10 times.
在这篇文章中,一种方法来产生自组装环钯化聚噻吩亚胺单层(表示为ITO@Pd-CPTIMs)被描述。采用自组装(SA)、杂化掺杂(HD)和电化学聚合(ECP)相结合的方法制备单层膜,称为SA-HD-ECP。通过在电化学聚合过程中使用不同的噻吩衍生物、浓度和扫描次数来调节杂化掺杂的结构和形态,提高了铃木偶联反应中聚合单层膜的催化活性和稳定性。研究了催化表面的形态变化与催化活性的关系。ITO@Pd-PTF可以提高催化活性,具有较高的TON值(45000 mol/molcat),达到至少10次的循环能力。
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引用次数: 1
Acetonitrile Combustion over Copper-Based Nanocatalysts: A Structure-Performance Relationship Study 乙腈在铜基纳米催化剂上燃烧:结构-性能关系研究
Pub Date : 2021-12-01 DOI: 10.21926/cr.2201002
J. A. P. Ponciano, M. S. Batista
In this paper, the relationship between activity and structure of Cu2+ in different chemical environments of Cu-BETA, La2CuO4, and CuO nanocatalysts was systematically investigated for acetonitrile combustion. The study revealed that exchanged and octahedral species of Cu2+ coexist in Cu-BETA, while octahedral species are dominant in CuO and La2CuO4. All nanocatalysts achieved high conversion rates of acetonitrile, which rapidly increased with temperature. CuO and La2CuO4 led to the formation of undesired products such as N2O and NO. On the other hand, Cu-BETA showed high acetonitrile conversion along with a high N2 yield. The excellent performance of Cu-BETA can be attributed to the easy reducibility of the highly dispersed Cu-species and the small crystallite size. Cu-BETA also exhibited exceptional stability. Therefore, the high conversion rate and the high N2 yield make Cu-BETA a promising catalyst for acetonitrile combustion.
本文系统研究了Cu-BETA、La2CuO4和CuO纳米催化剂在乙腈燃烧中不同化学环境下Cu2+活性与结构的关系。研究发现Cu-BETA中Cu2+的交换态和八面体态共存,而CuO和La2CuO4中以八面体态为主。所有纳米催化剂的乙腈转化率都很高,且随温度的升高而迅速提高。CuO和La2CuO4导致N2O和NO等不良产物的生成。另一方面,Cu-BETA表现出高的乙腈转化率和高的N2收率。Cu-BETA具有优异的性能,可归因于其高度分散的cu易于还原性和小晶粒尺寸。Cu-BETA也表现出优异的稳定性。因此,高转化率和高N2产率使Cu-BETA成为一种很有前途的乙腈燃烧催化剂。
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引用次数: 1
Determining the Band Alignment at the BiVO4|NiOOH Interface Using the Hybrid DFT Technique 利用混合DFT技术确定BiVO4|NiOOH界面的波段对准
Pub Date : 2021-11-29 DOI: 10.21926/cr.2201005
J. Conesa
It is important to understand the band offsets between semiconductors, which are crucial to determine the direction of electron transfer at the interfaces. Two methods are normally used to determine the direction from the first principles: alternating slabs put in contact (without empty spaces between them) and separate calculations for each material surface in the presence of vacuum spaces. The first method may introduce distortions due to insufficient epitaxial match, which may lead to bandgap changes, and the second may neglect electron transfer at the interface, which may be important in systems exhibiting very different average electronegativities. This can also imply a spill of electronic density into the vacuum spaces, which will not be present at real interfaces. Herein, both approaches were used to study the BiVO4/NiOOH interface, and the results were compared; the results are here relevant for photoelectrochemistry. The method is based on hybrid Density Functional Theory methods which give for the bulk phases Bandgap values that agree with the experimental ones (in one case, a value reflecting the theoretical value). The distances between the (hybrid DFT-derived) band positions and the corresponding profiles of the Hartree electrostatic potential were transferred to the interfaces. This helps determining the appropriate positions of the valence and conduction bands (as has been suggested by C. G. Van de Walle & R. M. Martin, Phys. Rev. B 1987, 35, 8154). It is ensured that the interfaces are nonpolar (Tasker’s criterion: P.W. Tasker, J. Phys. C: Solid State Phys. 1979, 12, 4977).
了解半导体之间的带偏移是很重要的,这对于确定界面上电子转移的方向至关重要。通常有两种方法用于根据第一原理确定方向:交替放置接触的板料(它们之间没有空白空间)和在存在真空空间的情况下对每个材料表面进行单独计算。第一种方法可能由于外延匹配不足而导致扭曲,这可能导致带隙变化,第二种方法可能忽略了界面上的电子转移,这在具有非常不同的平均电负性的系统中可能很重要。这也可能意味着电子密度溢出到真空空间中,而这在实际界面中是不存在的。本文采用两种方法对BiVO4/NiOOH界面进行了研究,并对研究结果进行了比较;这里的结果与光电化学有关。该方法基于混合密度泛函理论方法,给出了与实验值一致的体相带隙值(在一种情况下,一个值反映了理论值)。混合dft导出的能带位置之间的距离和相应的哈特里静电势分布被传递到界面上。这有助于确定价带和导带的适当位置(如C. G. Van de Walle和R. M. Martin, Phys所建议的)。Rev. B 1987, 35, 8154)。保证了界面是非极性的(Tasker准则:P.W. Tasker, J. Phys。[j] .固体物理学报,1999,12(2):481 - 481。
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引用次数: 0
Versatility of Supported Gold Nanoparticles on Hydrotalcites used for Oxidation and Reduction Reactions 用于氧化和还原反应的水滑石上负载的金纳米颗粒的多功能性
Pub Date : 2021-10-25 DOI: 10.21926/cr.2201001
Fabien Drault, Y. Snoussi, Camila P. Ferraz, J. Thuriot-Roukos, S. Heyte, I. I. Júnior, Maya Marinova, S. Paul, R. Wojcieszak
Regardless of their size, supported gold nanoparticles are largely used for liquid-phase oxidation reactions. Small gold nanoparticles exhibit good performance during the reduction of organic compounds. The direct reduction of carboxylic acid to aldehyde is a famous and familiar reaction in the field of organic chemistry and is considered as one of the fundamental chemical transformations. Herein, we present Au/hydrotalcite, Au/MgO, and Au/Al2O3 systems as heterogeneous versatile catalysts to realize the oxidation of furfural (FF) to furoic acid (FA) and realize the reduction of FA to FF. Experiments showed that in standard aqueous conditions under air, FF can be easily oxidized to FA. When DMSO was used as a solvent to conduct the experiments under an atmosphere of CO2, FA was reduced to FF. The Au/HT series of catalysts was found to be active in both transformations, pointing out the versatility of the gold-based catalysts. The activity significantly depends on the acid-base properties of the catalyst.
不管它们的大小如何,支撑金纳米颗粒主要用于液相氧化反应。小的金纳米颗粒在有机化合物的还原过程中表现出良好的性能。羧酸直接还原成醛是有机化学领域中一个著名而熟悉的反应,被认为是基本的化学转化之一。本文采用Au/水滑石、Au/MgO和Au/Al2O3体系作为多相多用途催化剂,实现糠醛(FF)氧化生成糠酸(FA),并将FA还原为FF。实验表明,在空气条件下的标准水溶液条件下,FF很容易被氧化为FA。以DMSO为溶剂,在CO2气氛下进行实验,FA被还原为FF。Au/HT系列催化剂在这两种转化中均表现出活性,表明了金基催化剂的通用性。活性很大程度上取决于催化剂的酸碱性质。
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引用次数: 1
Effect of Acid Treatment on the Properties of Zeolite Catalyst for Straight-Run Gasoline Upgrading 酸处理对直馏汽油沸石催化剂性能的影响
Pub Date : 2021-10-10 DOI: 10.21926/cr.2104004
L. Velichkina, Ya. E. Barbashin, A. Vosmerikov
The objective of this research was to analyze the effect of different concentrations of nitric and hydrochloric acids on the structural, acidic, and catalytic properties of a post-synthetic treated ZSM-5 type zeolite at various temperatures. The properties of zeolite catalysts were determined using different methods, such as the Brunauer-Emmett-Teller (BET) method for specific surface area, temperature-programmed desorption (TPD) of ammonia method for acidic properties, and a flow-through unit with fixed bed catalyst (with upgrading straight-run gasoline fraction of oil) for catalytic activities of initial zeolite and acid-treated samples. The structural and acidic properties of both untreated and treated zeolites were investigated, and the effect of acid treatment on the catalytic properties of the samples in the course of upgrading the straight-run gasoline fraction of oil was determined. The post-synthetic treatment with aqueous nitric acid increased the specific surface area and volume of micropores of ZSM-5 zeolite, while the treatment with aqueous hydrochloric acid led to the formation of mesopores. Acid treatments of zeolite decreased the number of acid sites, mainly due to diminished concentration of low-temperature sites. The yield of liquid products in the conversion of straight-run gasoline fraction of oil, i.e., generation of high-octane gasolines with improved environmental features, was increased using acid-treated zeolites, which was due to the decrease in arene content.
本研究的目的是分析不同浓度的硝酸和盐酸对合成后处理的ZSM-5型沸石在不同温度下的结构、酸性和催化性能的影响。采用不同的方法测定沸石催化剂的性质,如比表面积的brunauer - emmet - teller (BET)法、酸性性质的程序化氨温度解吸(TPD)法,以及初始沸石和酸处理样品的催化活性的固定床催化剂(升级汽油馏分)的流动装置。研究了未经处理和处理的沸石的结构和酸性,并测定了酸处理对油中直馏汽油馏分提质过程中样品催化性能的影响。合成后硝酸水溶液处理增加了ZSM-5分子筛微孔的比表面积和体积,而盐酸水溶液处理导致中孔的形成。酸处理降低了沸石酸位的数量,主要是由于低温位的浓度降低。酸处理沸石降低了芳烃含量,提高了原油直馏汽油馏分转化过程中液体产品的收率,即生产环境性能更好的高辛烷值汽油。
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引用次数: 1
Photocatalytic Degradation of Azo Dyes Using Microreactors: Mechanistic Study of its Effects on H2O2 Addition 微反应器光催化降解偶氮染料:对H2O2加成影响的机理研究
Pub Date : 2021-08-17 DOI: 10.21926/cr.2103002
Y. Murakami, Minato Nakamura
The photocatalytic reaction involved in TiO2 photocatalysis was investigated using a microreactor coated with TiO2 film on the glass plate attached on one side of the microreactor. It was confirmed that the effect of H2O2 on the photocatalytic degradation efficiency of azo dyes (acid orange 7, acid red 151, and acid yellow 23) was dependent on the polymorphs (anatase and rutile) of TiO2 coated on the glass plate of the UV-irradiated microreactor. Scavengers of holes (KI) and electrons (p-benzoquinone) were added to the solution of azo dyes, and their effects on the degradation efficiencies of the azo dye (acid orange 7) in the microreactor system were investigated. It was found that the electron scavengers of p-benzoquinone showed much larger effects on the photocatalytic degradation efficiency than the hole scavengers of KI. Based on these results, the mechanism of the photocatalytic degradation of the azo dyes in the presence of H2O2 was proposed.
采用在微反应器一侧附着玻璃板上涂覆TiO2膜的微反应器,对TiO2光催化反应进行了研究。结果表明,H2O2对偶氮染料(酸橙7、酸红151、酸黄23)光催化降解效率的影响取决于微反应器玻璃板上涂覆的TiO2的多晶型(锐钛矿和金红石)。在偶氮染料溶液中加入空穴清除剂(KI)和电子清除剂(对苯醌),研究了它们在微反应器系统中对偶氮染料(酸橙7)降解效率的影响。结果表明,对苯醌的电子清除剂对光催化降解效率的影响远大于KI的空穴清除剂。在此基础上,提出了H2O2存在下光催化降解偶氮染料的机理。
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引用次数: 0
Stability of a Fe-Rich Cathode Catalyst in an Anion Exchange Membrane Fuel Cell 富铁阴极催化剂在阴离子交换膜燃料电池中的稳定性研究
Pub Date : 2021-06-09 DOI: 10.21926/cr.2103003
Lin Xie, D. Kirk
Fe-rich alloys have been widely studied as catalyst materials for the cathodic oxygen reduction reaction (ORR) in hydrogen fuel cells, and many have shown high activities. The stability of Fe-rich catalysts has also been researched, and some studies have shown promising results using an accelerated stress test (AST), which uses a potential cycling method. However, for commercial fuel cell applications, such as standby power systems, the catalyst has to tolerate a high potential for a long period, which can not be represented by the AST test. In this paper, the cathode stability of a Fe-rich catalyst was studied using a standby cell potential of 0.9V, a potential shown to be challenging for the competing Pt catalysts. After 1500 hrs of testing, significant morphology changes of both the tested cathode and anode were found due to a Fe leaching process. Other alloy materials, including Ni, Cr, and Mn, were also found leached out along with the Fe species from the catalyst framework. The results are a cautionary note for using Fe based catalysts for AEMFC cathodes.
富铁合金作为氢燃料电池阴极氧还原反应(ORR)的催化剂材料得到了广泛的研究,许多富铁合金表现出较高的活性。富铁催化剂的稳定性也得到了研究,一些研究使用加速应力测试(AST)显示了有希望的结果,该测试使用潜在循环方法。然而,对于商业燃料电池应用,如备用电源系统,催化剂必须长时间承受高电位,这是AST测试无法代表的。本文研究了一种富铁催化剂在0.9V的待机电位下的阴极稳定性,这一电位对Pt催化剂来说是一个挑战。经过1500小时的测试,由于铁浸出过程,被测阴极和阳极的形貌都发生了明显的变化。其他合金材料,包括Ni、Cr和Mn,也被发现与Fe一起从催化剂框架中浸出。该结果对使用铁基催化剂制备AEMFC阴极具有警示意义。
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引用次数: 0
Development of an Efficient Bi-Functional Catalyst made of a Novel Hybrid Material for Rechargeable Zn-Air Battery 可充电锌空气电池用新型混合材料高效双功能催化剂的研制
Pub Date : 2021-05-24 DOI: 10.21926/cr.2103001
Shiping Wang, G. Bendt, S. Schulz
One-pot synthesis of mesoporous hybrid material consisting of Mn-Co/CoO nanoparticles encapsulated in an N-doped graphene shell decorated with Mo2C nanoparticles (Mo2C-NC@Mn-Co/CoO) was reported. The Mn and Mo components synergistically refined the graphitized carbons due to the interactions with N and C atoms while promoting the stability of the Co/CoO nanoparticles. These components exhibited a beneficial effect on the dispersion of the active metal/metal oxide nanoparticles and the formation of a mesoporous structure under high-temperature conditions, which together led to optimized oxygen adsorption/desorption capabilities as well as mass transport properties. The hybrid material showed high bifunctional performance for both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), as well as promising catalytic properties as the air electrode in a zinc-air battery, featuring superior long-term cycle stability comparable to that of Pt-C/RuO2 materials.
报道了一锅法制备了Mn-Co/CoO纳米颗粒包裹在以Mo2C纳米颗粒(Mo2C-NC@Mn-Co/CoO)修饰的n掺杂石墨烯壳内的介孔杂化材料。Mn和Mo组分通过与N和C原子的相互作用协同细化了石墨化碳,同时促进了Co/CoO纳米颗粒的稳定性。这些成分对活性金属/金属氧化物纳米颗粒的分散和高温条件下介孔结构的形成都有有益的影响,这共同导致了优化的氧吸附/解吸能力和质量传输性能。该杂化材料具有良好的析氧反应(OER)和氧还原反应(ORR)双功能,作为锌-空气电池空气电极具有良好的催化性能,具有可与Pt-C/RuO2材料相比较的长期循环稳定性。
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引用次数: 0
Coating Composition on the Basis of Carbamide-PhenolFormaldehyde Co-Oligomer 基于酰胺-酚醛共聚物的涂料组成
Pub Date : 2021-03-31 DOI: 10.35702/catalres.10001
Naibova Tm, Musazadeh Zm
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引用次数: 0
期刊
Catalysis Research
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