Insights into the size effect of ZnCr_(2)O_(4)spinel oxide in composite catalysts for conversion of syngas to aromatics

Direct conversion of syngas to aromatics(STA)over oxide-zeolite composite catalysts is promising as an alternative method for aromatics production.However,the structural effect of the oxide component in composite catalysts is still ambiguous.Herein,we investigate the size effect by selecting ZnCr_(2)O_(4)spinel,as a probe oxide,mixing with H-ZSM-5 zeolite as a composite catalyst for STA reaction.The CO conversion,aromatics selectivity and space-time yield(STY)of aromatics are all significantly improved with the crystal size of ZnCr_(2)O_(4)oxide decreases,which can mainly attribute to the higher oxygen vacancy concentration and thus the rapid generation of more C1oxygenated intermediate species.Based on the understanding of the size-performance relationship,ZnCr_(2)O_(4)-400 with a smaller size mixing with H-ZSM-5 can achieve32.6%CO conversion with 76%aromatics selectivity.The STY of aromatics reaches as high as 4.79 mmol g_(cat)^(-1)h^(-1),which outperforms the previously reported some typical catalysts.This study elucidates the importance of regulating the size of oxide to design more efficient oxidezeolite composite catalysts for conversion of syngas to value-added chemicals.

Electronic Structure of the Weak Topological Insulator Candidate Zintl Ba_(3)Cd_(2)Sb_(4)

One of the greatest triumph of condensed matter physics in the past ten years is the classification of materials by the principle of topology.The existence of topological protected dissipationless surface state makes topological insulators great potential for applications and hotly studied.However,compared with the prosperity of strong topological insulators,theoretical predicted candidate materials and experimental confirmation of weak topological insulators(WTIs) are both extremely rare.By combining systematic first-principles calculation and angle-resolved photoemission spectroscopy measurements,we have studied the electronic structure of the dark surface of the WTI candidate Zintl Ba_(3)Cd_(2)Sb_(4)and another related material Ba_(3)Cd_(2)As_(4).The existence of two Dirac surface states on specific side surfaces predicted by theoretical calculations and the observed two band inversions in the Brillouin zone give strong evidence to prove that the Ba_(3)Cd_(2)Sb_(4)is a WTI.The spectroscopic characterization of this Zintl Ba_(3)Cd_(2)N_(4)(N = As and Sb) family materials will facilitate applications of their novel topological properties.

用于人工肌肉纤维丝的“三明治”复合结构熔融机理仿真

研究了构成“三明治”结构的聚甲基丙烯酸甲酯(PMMA)/聚乙烯(PE)/环烯烃类共聚物弹性体(COCe)3种材料在不同温度场的熔融机理和成型过程,为后续人工肌肉纤维丝的制作提供数据参考。建立了基于标准κ-ε湍流模型的分段加热有限元仿真模型,通过设置不同参数对比研究进料速度、单元划分方式和边界条件设置对仿真结果的影响,实现高分子材料加热熔融凝固过程的仿真模拟。仿真结果表明,通过面映射和局部加密处理的方式划分网格得到的计算结果精度较高;控制进料速度约1mm/s时,材料能够得到充分加热,密度达到稳定,有利于材料的挤出成型。

Formaldehyde intermediate participating in the conversion of methanol to aromatics over zinc modified H-ZSM-5

Metal-modified H-ZSM-5 has a high selectivity of aromatics in methanol to aromatics(MTA)reaction,which is often attributed to the metal promoting the aromatization of intermediate olefins.However,the effect of methanol dehydrogenation on aromatics formation over these catalysts is rarely studied.Here,we report that HCHO,which is formed by methanol dehydrogenation over Zn/H-ZSM-5 prepared by Zn impregnation,can participate in the synthesis of aromatics.Methanol conversion can produce more aromatics than olefins(propylene or ethylene)conversion over Zn/H-ZSM-5,indicating the conventional MTA pathway including methanol-to-olefins and olefins-to-aromatics is not complete.Moreover,an MTA mechanism including the conventional pathway and the methanol and HCHO coupling pathway is systematically proposed.

HZSM-35 zeolite catalyzed aldol condensation reaction to prepare acrylic acid and its ester:Effect of its acidic property

Acrylic acid(AA)and its ester,methyl acrylate(MA),were produced by a green one‐step aldol condensation reaction of dimethoxymethane and methyl acetate.The reaction was conducted over ZSM‐35 zeolites with different concentrations of Bronsted acid,which were prepared by the sodium ion‐exchange process with H‐form zeolite.The acidic property of HZSM‐35 was studied in detail through infrared experiments.About 51%of all bridging OH groups were distributed in cages,while 23%and 26%,respectively,were distributed in 10‐and 8‐ring channels.The catalytic performance was enhanced by a high concentration of Bronsted acid,indicating that Bronsted acid is an active site for the aldol condensation reaction.The ZSM‐35 zeolite possessing a concentration of Bronsted acid as high as 0.049 mmol/g demonstrated excellent performance with a MA+AA selectivity of up to 73%.

Catalytic activity of Cu/ZnO catalysts mediated by MgO promoter in hydrogenation of methyl acetate to ethanol

Hydrogenation of methyl acetate is a key step in ethanol synthesis from dimethyl ether carbonylation and Cu-based catalysts are widely studied.We report here that the hydrogenation activity of Cu/ZnO catalysts can be enhanced by the addition of MgO promoter.The evolution of crystal phases during coprecipitation and the physicochemical properties of calcined and reduced catalysts by X-ray diffraction(XRD),thermogravimetric(TG)-mass spectrometry(MS),Brunauer-Emmett-Teller(BET),transmission electron microscopy(TEM),N_(2)O titration,in situ CO-Fourier transform infrared spectroscopy(FTIR)and H_(2)-temperature programmed reduction(H_(2)-TPR)reveal that the promoter effect likely lies in the presence of Mg^(2+).A proper amount of Mg^(2+)mediates the precipitation process of Cu and Zn,leading to preferable formation of aurichalcite(Cu_(x)Zn_(1-x))5(CO_(3))_(2)(OH)_(6) crystal phase and a small amount of basic carbonates such as hydrozincite Zn_(5)(CO_(3))_(2)(OH)_(6) and malachite Cu_(2) CO_(3)(OH)_(2).The presence of aurichalcite strengthens the interaction between Cu and Zn species,and thus enhances the dispersity of CuO species and helps generation of Cu^(+)species on reduced catalysts.Furthermore,the performance of Cu/ZnO catalysts exhibits an optimal dependence on the Mg loading,i.e.,17.5%.However,too much Mg^(2+)in the precipitation liquid prohibits formation of aurichalcite but enhances formation of basic nitrates,leading to a dramatically reduced hydrogenation activity.These findings may find applications for optimization of other Cu-based catalysts in a wider range of hydrogenation reactions.

Achieving high conversion of syngas to aromatics

Realizing high CO conversion and high aromatics selectivity simultaneously in syngas-to-aromatics(STA)reaction is still challenging.Herein,we report a 57.5%CO conversion along with 74%aromatics selectivity over a composite catalyst consisting of Fe/ZnCr_(2)O_(4)(Fe modified ZnCr_(2)O_(4)spinel)oxide and H-ZSM-5 zeolite.Impregnation of only 3 wt%of Fe onto ZnCr_(2)O_(4)can remarkably increase CO conversion without sacrificing the aromatics selectivity.Oxygen vacancy concentration is improved after impregnating Fe.The highly dispersed iron carbide species is formed during the reaction over Fe/ZnCr_(2)O_(4)spinel oxide.The synergistic effect of oxygen vacancy and iron carbide results in a rapid formation of abundant oxygenated intermediate species,which can be continuously transformed to aromatics in H-ZSM-5.This study provides a new insight into the design of highly efficient catalyst for syngas conversion.

One‐step aldol condensation reaction of dimethoxymethane and methyl acetate over supported Cs/ZSM‐35 zeolite catalysts

This study was performed for the development of a green and promising approach for the synthesis of methyl acrylate and acrylic acid by a one‐step aldol condensation reaction of dimethoxymethane and methyl acetate over cesium oxide‐supported on ZSM‐35 zeolite catalysts; the effect of base sites as well as acid sites on the aldol condensation reaction was studied in detail. It was found that base sites were harmful for aldol condensation due to their failure in catalyzing the decomposition of dimethoxymethane precursor into formaldehyde, whereas the acid site was indispensable for the reaction to proceed. This reaction cannot take place without an acid site. Although acid sites in H‐form of the zeolite（HZSM‐35） are indispensable for the aldol condensation reaction, not all of them tend to favor this reaction. A strong acid catalyzes methanol‐to‐olefin‐like reactions resulting in hydrocarbon byproducts, which are finally transferred to hard coke. Medium strong acids and weak acids are great candidates for the target aldol condensation reaction with high activity and selectivity. A γ‐Al2O3 sample with abundant weak‐strength Lewis acid sites, together with a few medium‐strong‐strength acid sites, performs well with a high activity and considerable stability during the synthesis of methyl acrylate and acrylic acid.

Conversion of CO_(2) and H_(2) into propane over InZrO_(x) and SSZ-13 composite catalyst

Direct converting carbon dioxide into hydrocarbon fuels and value-added chemicals would offer a very attractive approach for efficient utilization of CO_(2) as a carbon resource.Although,olefins,aromatics and gasoline have been successfully synthesized by CO_(2) hydrogenation,highly selective conversion of CO_(2) and H_(2) into C_(2+)hydrocarbon is still challenging due to a high C-C coupling barrier and inhibiting the production of other long-chain hydrocarbons.Here,we report a composite catalyst made of InZrO_(x) and SSZ-13 molecular sieve(InZrO_(x)+SSZ-13),which exhibits 74.5% propane selectivity at 623 K.The 8-MR micropores and the higher strength of the acid for SSZ-13 benefit the formation of propane.Compared with pure InO_(x) and m-ZrO_(2) the composite oxide InZrO_(x) containing more oxygen vacancies,exhibits to be more readily reduced by H_(2) and easier to adsorb and desorb CO_(2) within the reaction temperature.All those could be beneficial to the activation and conversion of H_(2) and CO_(2).The catalytic performance of InZrO_(x)+SSZ-13 in CO_(2) hydrogenation provides a potential for production of propane.

Insights into effects of ZrO_(2) crystal phase on syngas‐to‐olefin conversion over ZnO/ZrO_(2) and SAPO‐34 composite catalysts

The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.

The carboxylates formed on oxides promoting the aromatization in syngas conversion over composite catalysts

Syngas to aromatics(STA)over bifunctional catalysts has attracted much attention in recent years,but the mechanism underlying the formation of aromatics remains controversial.The critical reaction intermediates,carboxylates,were first identified and then confirmed to essentially promote aromatization in the syngas conversion over a ZnCrAlO_(x)&H-ZSM-5 composite catalyst.This study provides evidence that the carboxylates can be formed during the reactions of formate species and olefins.In addition,it is shown that the carboxylates favor the formation of aromatics over H-ZSM-5 even in the presence of H2.A novel mechanism for the formation of aromatics via the generation and transformation of carboxylate intermediates is proposed,and the transformation of carboxylates to aromatics via methyl-2-cyclopenten-1-one(MCPO)intermediates is indeed likely.A better understanding of the formation mechanism of aromatics would help optimize the composite catalyst.

Highly converting syngas to lower olefins over a dual-bed catalyst

Light olefins (C2–C4olefins) are the most important basic carbon-based building blocks, which are mainly produced from the catalytic cracking of naphtha [1–3]. With the rapid depletion of oil reserves and the growing demand for lower olefins, there is an urgent need to develop an alternative technique for producing them from non-petroleum resources such as coal, natural gas, or biomass. Currently, coal has been successfully transformed to olefins in China via the combination of the processes of coal-tosyngas, syngas-to-methanol and methanol-to-olefins [4–6]. In order to further improve efficiency and reduce investment, the direct conversion of syngas to olefins has received extensive attention in recent years [7].

Magnetotransport Properties of a Nodal Line Semimetal TiSi

We report the magnetoresistance（MR）, de Haas-van Alphen（dHvA） effect and Hall effect measurements on a single crystal of TiSi, which is predicted to be a nodal line semimetal. With application of a magnetic field, a metal-to-insulator-like transition in ρ（T） and a nonsaturating MR are observed at low temperatures. The dHvA oscillations reveal a small Fermi-surface pocket with a nontrivial Berry phase. The analysis of the nonlinear Hall resistivity shows that TiSi is a multiband system with low carrier densities and high mobilities. All these results unambiguously prove the existence of Dirac fermions in TiSi.

Superconductivity at the Normal Metal/Dirac Semimetal Cd3As2 Interface

We investigate the interface between a three-dimensional Dirac semimetal Cd3As2 and a normal metal via softpoint contact spectroscopy measurement.The superconducting gap features were detected below 3.8 K and 7.1 K in the case of Cd3As2 single crystals sputter-coated with the Pt and Au films,respectively,in the differential conductance dI/dV-V plots of the point contacts.As the applied magnetic field increased,the drop in the zerobias contact resistance shifted toward lower temperatures.The topologically non-trivial band structure of Cd3As2 is considered to play a crucial role in inducing the superconductivity.Apart from realizing superconductivity in topological materials,our creative approach can be used to investigate possible topological superconductivity and exhibits a high application potential in electronic devices.

A dual-bed catalyst for producing ethylene and propylene from syngas

Ethylene and propylene(C_(2)^(–)3=)are the two most demanded olefin products,which are mainly produced by thermal and catalytic cracking of petroleum-derived hydrocarbons now[1].With the depletion of petroleum resources,the use of non-petroleum resources such as natural gas,coal,biomass,even CO_(2)etc.

Small tracking error correction for moving targets of intelligent electro-optical detection systems

Small tracking error correction for electro-optical systems is essential to improve the tracking precision of future mechanical and defense technology.Aerial threats,such as“low,slow,and small(LSS)”moving targets,pose increasing challenges to society.The core goal of this work is to address the issues,such as small tracking error correction and aiming control,of electro-optical detection systems by using mechatronics drive modeling,composite velocity–image stability control,and improved interpolation filter design.A tracking controller delay prediction method for moving targets is proposed based on the Euler transformation model of a two-axis,two-gimbal cantilever beam coaxial configuration.Small tracking error formation is analyzed in detail to reveal the scientific mechanism of composite control between the tracking controller’s feedback and the motor’s velocity–stability loop.An improved segmental interpolation filtering algorithm is established by combining line of sight(LOS)position correction and multivariable typical tracking fault diagnosis.Then,a platform with 2 degrees of freedom is used to test the system.An LSS moving target shooting object with a tracking distance of S=100 m,target board area of A=1 m^(2),and target linear velocity of v=5 m/s is simulated.Results show that the optimal method’s distribution probability of the tracking error in a circle with a radius of 1 mrad is 66.7%,and that of the traditional method is 41.6%.Compared with the LOS shooting accuracy of the traditional method,the LOS shooting accuracy of the optimized method is improved by 37.6%.

一种在室温附近具有高热电性能的准一维块体材料

在低维材料体系中探索高热电性能是热电材料研究领域的一个重要方向.实际上,近年来所发现的热电材料中的很大一部分,比如Bi_(2)Te_(3),SnSe,Mg_(3)Sb_(2)等,都具有准二维晶体结构.但是,到目前为止对准一维材料的热电研究还非常少见.本文报道了一种在室温附近具有高热电性能的准一维块体材料:TLCu_(3)Te_(2).在室温下,该材料沿单晶针状方向具有高达1.3的热电优值;在400 K时,其热电优值甚至可以达到1.5,一定程度超越了目前该温区的商用材料热电性能.通过详细的热电输运实验并结合第一性原理计算,作者发现TlCu_(3)Te_(2)的高热电优值主要起源于饼状费米口袋的高度各向异性准一维电子色散关系带来的大热电功率因子,以及准一维重元素复杂晶格导致的极低热导率.该研究表明准一维块体材料中的单轴性热电效应是一个值得深入探索的热电材料新领地.

Large transverse thermoelectric figure of merit in a topological Dirac semimetal

The Seebeck effect encounters a few fundamental constraints hindering its thermoelectric(TE)conversion efficiency.Most notably,there are the charge compensation of electrons and holes that diminishes this effect,and the Wiedemann-Franz(WF)law that makes independent optimization of the corresponding electrical and thermal conductivities impossible.Here,we demonstrate that in the topological Dirac semimetal Cd3As2 the Nernst effect,i.e.,the transverse counterpart of the Seebeck effect,can generate a large TE figure of merit zNT.At room temperature,zNT≈0.5 in a small field of 2 T and it significantly surmounts its longitudinal counterpart for any field.A large Nernst effect is generically expected in topological semimetals,benefiting from both the bipolar transport of compensated electrons and holes and their high mobilities.In this case,heat and charge transport are orthogonal,i.e.,not intertwined by the WF law anymore.More importantly,further optimization of zNT by tuning the Fermi level to the Dirac node can be anticipated due to not only the enhanced bipolar transport,but also the anomalous Nernst effect arising from a pronounced Berry curvature.A combination of the topologically trivial and nontrivial advantages promises to open a new avenue towards high-efficient transverse thermoelectricity.

High-throughput sequencing detection and ensartinib treatment of lung cancer harboring NTRK1 fusion

Dear Editor,Although fusion events involving neurotrophic receptor tyrosine kinase 1,2,and 3 genes(NTRK1,NTRK2,and NTRK3,encoding TRKA/B/C respectively)were found in diverse tumor types,only 0.1%-0.3%of lung cancer patients harbor an NTRK(and mostly NTRK1)fusion as the primary oncogenic event[1].Such low prevalence may be partially due to the limited availability of first-line assays for detecting rare fusion events[2].Immunohistochemistry is limited by sensitivity and variable tissue background,and fluorescence in-situ hybridization falls short of elucidating functional significance such as the identity of the partner or structure of the transcript.While DNA next-generation sequencing(NGS)is suitable for mutation calling(single nucleotide variation[SNV]and insertion-or-deletion[indel]),and RNA NGS is particularly effective in detecting fusions[3],routinely performing these two assays together is labor-intensive.As a solution,we have developed a single NGS assay(PANO-Seq)for unified RNA/DNA target enrichment library preparation[4],which takes about 12 hours and $10 to prepare.