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.

Modeling and Analysis of the Impacts of Temporal-Spatial Variant Troposphere on Ground-Based SAR Imaging of Asteroids

The near-Earth asteroid collisions could cause catastrophic disasters to humanity and the Earth,so it is crucial to monitor asteroids.Ground-based synthetic aperture radar(SAR)is an observation technique for high resolution imaging of asteroids.The ground-based SAR requires a long integration time to achieve a large synthetic aperture,and the echo signal will be seriously affected by temporal-spatial variant troposphere.Traditional spatiotemporal freezing tropospheric models are ineffective.To cope with this,this paper models and analyses the impacts of temporal-spatial variant troposphere on ground-based SAR imaging of asteroids.For the background tropo-sphere,a temporal-spatial variant ray tracing method is proposed to trace the 4D(3D spatial+temporal)refractive index network provided by the numerical weather model,and calculate the error of the background troposphere.For the tropospheric turbulence,the Andrew power spectral model is used in conjunction with multiphase screen theory,and varying errors are obtained by tracking the changing position of the pierce point on the phase screen.Through simulation,the impact of temporal-spatial variant tropospheric errors on image quality is analyzed,and the simulation results show that the X-band echo signal is seriously affected by the troposphere and the echo signal must be compensated.

3D Target Localization Based on FrFT from Spaceborne Curve SAR

Synthetic aperture radar(SAR)three-dimensional(3D)imaging technology can reconstruct the complete structure of observed targets and has been a hot topic.Compared with tomographic SAR,array interferometric SAR,and circular SAR,curve SAR can use less data to achieve 3D positioning of targets.Most existing algorithms for estimating Doppler frequency modulation(FM)rate are based on sub aperture partitioning,resulting in low computational efficiency.To address this,this article establishes a target height estimation model,which reflects the relation-ship between the height and the residual Doppler FM rate for spaceborne curve SAR.Then,a fast SAR 3D localization processing flow based on fractional Fourier transform(FrFT)is proposed.Experimental verification demonstrates that this method can estimate the Doppler FM of the target column by column,and the 3D position error for non-overlapping targets is controlled within 1 m.For overlapping points with an intensity ratio greater than 1.5,the root mean square error(RMSE)of the estimation results is around 5 m.If the separation between overlapping points is greater than 35 m,the RMSE decreases to approximately 2 m.

SAR Tomography with Improved Non-Local Means Filtering Based on Adaptive Window

In order to mitigate speckle noise in synthetic aperture radar(SAR)images and enhance the accuracy of SAR tomography,non-local means(NL-means)filtering has been proven to be an effective method for improving the quality of SAR interferograms.Apart from considerations like noise type and the definition of similarity,the size and shape of filtering windows are critical factors influencing the efficacy of NL-means filtering,yet there has been limited research on this aspect.This paper introduces an enhanced NL-means filtering method based on adaptive windows,allowing for the automatic adjustment of filtering window size according to the amplitude information of the SAR interferogram.Simultaneously,a directional window is incorporated to align SAR interferograms,achieving the dual objective of preserving filtering standards and retaining detailed information.Experimental results on interferogram filtering and tomography,based on TerraSAR-X data,demonstrate that the proposed method effectively reduces phase noise while maintaining texture accuracy,thereby improving tomography quality.

ZrO_(2)晶相对ZnO/ZrO_(2)+SAPO-34双功能催化剂上合成气制烯烃反应的影响

烯烃是重要的化工原料,目前主要通过石油催化裂化得到.随着石油资源的消耗以及人们对烯烃需求的日益增长,开发非石油路线制取烯烃势在必行.合成气可以从煤、天然气和生物质等获得,由合成气作为重要的C1平台分子一步制取烯烃(STO)的过程受到了广泛关注.将合成气制甲醇/二甲醚的金属催化剂与甲醇制烯烃的分子筛催化剂耦合得到的混合双功能催化剂,可以使合成气高选择性地转化为烯烃.其中,ZnO/ZrO_(2)金属氧化物催化剂被广泛应于合成气的活化,然而,该金属氧化物结构对混合双功能催化剂上合成气制烯烃反应的影响尚不明确.本文合成了单斜相ZrO_(2)(m-ZrO_(2))和四方相ZrO_(2)(t-ZrO_(2)),并负载ZnO制成催化剂,再将其与SAPO-34分子筛物理混合得到混合双功能催化剂,用于合成气制烯烃反应中.在较优化的条件下,ZnO/m-ZrO_(2)与SAPO-34分子筛组成的双功能催化剂CO转化率为27.9%,低碳烯烃选择性高达80.5%,性能明显优于ZnO/t-ZrO_(2)+SAPO-34双功能催化剂.为研究ZrO_(2)晶相对催化合成气制烯烃反应性能的影响,对ZnO/ZrO_(2)进行红外光谱表征.结果表明,ZnO/m-ZrO_(2)较ZnO/t-ZrO_(2)具有更多的表面羟基和更多的路易斯酸性位点.金属氧化物表面的路易酸主要与催化剂表面不饱和的金属离子有关,而且Zr基催化剂表面羟基有助于缺陷氧的形成,因此,ZnO/m-ZrO_(2)催化剂表面应该具有更高浓度的氧缺陷位.光电子能谱进一步证明了ZnO/m-ZrO_(2)表面有更高浓度的氧缺陷位.另外,Zr基催化剂上表面羟基还有利于CO与其形成羧酸盐物种,在623-673 K条件下的CO原位吸附的红外光谱表明,ZnO/m-ZrO_(2)催化剂上CO吸附的浓度及其表面羧酸盐浓度均明显高于ZnO/t-ZrO_(2)催化剂,这与ZnO/m-ZrO_(2)表现出更好的催化合成气转化性能一致.为了探究该催化剂体系上合成气制烯烃的反应路径,分别对两种晶相的ZnO/ZrO_(2)和相应的双功能催化剂进行了原位红外监测.与CO红外漫反射相比,合成气氛围下金属氧化表面除了存在吸附态的CO和甲酸盐物种,还存在表面甲氧基物种,后者是合成气制甲醇/二甲醚过程重要的中间物种.对合成气制烯烃过程中分子筛上的停留物种进行分析,结果发现,停留物种中含有多甲基苯、多甲基萘等甲醇制烯烃过程中的烃池物种.另外,合成气氛围下双功能催化剂甲氧基信号峰明显弱于金属氧化物表面甲氧基的信号强度,表明STO过程应该是合成气制甲醇/二甲醚与甲醇制烯烃的串联过程.综上所述,在STO反应中,相较于ZnO/t-ZrO_(2)催化剂,ZnO/m-ZrO_(2)催化剂具有更高浓度的表面羟基物种、路易斯酸密度和表面氧缺陷位,从而有利于羧酸盐及甲氧基中间物种的形成,进而提高了混合双功能催化剂催化STO反应性能.

金属氧化物催化剂上合成气转化中羧酸盐物种促进芳烃的生成

芳烃是重要的化工原料,目前主要通过石油催化裂化和催化重整制得.随着石油资源的消耗以及芳烃的需求日益增长,开发非石油路线制备芳烃势在必行.因此,从煤、天然气和生物质出发,经合成气一步制芳烃(STA)广受关注.将合成气制甲醇的金属催化剂和甲醇制芳烃的分子筛催化剂复合,可以制备双功能催化剂,用于合成气反应可高选择性得到芳烃.然而,关于此过程中芳烃的生成机理仍有争论.目前人们认为,生成芳烃的中间体主要分甲醇和其他含氧物种(乙烯酮,醛类)两种.本文以ZnCrAlO_(x)和H-ZSM-5为模型催化剂,进行合成气制芳烃、甲醇制芳烃和丙烯制芳烃反应,确定了传统的甲醇制芳烃路径不是合成气制芳烃中的主要途径,并通过原位傅里叶变换红外光谱和气相色质谱解释了STA反应中两种活性组分距离越近,芳烃选择性越高的原因,从而提出了在合成气制芳烃过程中芳烃的生成机理.通过比较双功能催化剂上合成气、甲醇以及丙烯的反应性能发现,在甲醇和丙烯转化时,其芳烃选择性远小于合成气转化时的,由此可认为,在合成气制芳烃的路径主要不经由传统的甲醇制芳烃,而是通过烯烃聚合脱氢生成芳烃.红外表征和共进料实验表明,合成气可以在金属催化剂表面生成甲酸盐物种,它可与烯烃反应生成羧酸盐物种,再迁移到分子筛上反应生成芳烃,且羧酸盐物种在分子筛上的芳构化能力要高于丙烯;即使在氢气氛围下,当丙烯的芳构化能力受到氢气极大抑制时,羧酸盐物种仍能高选择性生成芳烃.本文制备了一系列金属催化剂和分子筛物理接近距离不同的双功能催化剂,研究了合成气在双功能催化剂上制芳烃时,金属催化剂和分子筛二者组分的距离对芳烃选择性的影响.随着二者接近距离的增加,芳烃选择性急剧增加;通过GC-MS分析合成气转化时的停留物种,发现随着二者接近距离的增加,羧酸盐物种和甲基环戊烯酮的量明显增加,因此,羧酸盐物种和甲基环戊烯酮物种在生成芳烃中起到了重要的作用.综上所述,我们提出了STA中一条新的芳烃生成路径,并证明了羧酸盐物种是其中重要的中间物种.它经由金属表面的甲酸盐物种和烯烃反应生成,随后迁移到分子筛上生成甲基环戊烯酮物种,再脱水生成芳烃.

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.

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.

香茅油纳米乳剂的构建、表征、抗菌性能和细胞毒性

化学合成杀菌剂的大量、不合理使用对人类健康造成危害的同时也会导致严重的环境污染。因此,迫切需要寻找低毒、高效、无残留的天然杀菌剂。植物精油因其优良的杀菌活性、良好的生物相容性和丰富的来源,已成为农业病害防控领域的研究热点。香茅油是一种具有趋避、杀虫和抗菌活性的天然植物精油,主要包括香茅醛、香叶醇和香茅醇。目前,关于香茅油的研究主要集中于卫生害虫的驱避和防治,而用于农业致病菌防治的相关报道相对较少。在实际应用中,香茅油的疏水性和挥发性导致其生物利用度低,不能充分发挥生物活性。因此,构建一种改善香茅油疏水性、降低挥发性的递送系统十分必要。纳米乳剂因具有液滴细微均匀、物理稳定性好、渗透能力强以及生物利用度高等优点,已成为疏水农药的重要递送系统。本研究通过观察样品的外观和微观结构,并且测量样品液滴大小,考察了乳化剂种类(亲水亲油平衡值,HLB)、用量和乳化时间对纳米乳剂形成及稳定的影响,在此基础上筛选了香茅油纳米乳剂的优化配方。同时本研究还调查了香茅油纳米乳剂的生物活性和生物安全性。结果表明,以蓖麻油聚氧乙烯醚EL-40 (HLB=13.5)为乳化剂的纳米乳剂性能最佳,且乳化剂用量从3%增加到7%(w,质量分数)时,纳米乳剂稳定性提高。此外,高速剪切3min获得的纳米乳剂稳定性最高。基于此,确定了香茅油纳米乳剂的优化配方为:5%(w)香茅油,6%(w)乳化剂(EL-40),89%(w)去离子水,高速剪切3min。香茅油纳米乳剂对菠萝泛菌(Pantoeaananatis)具有良好的抑制作用,抑制中浓度(EC_(50))为74.85 mg·L^(-1)。纳米乳剂(低于100 mg·L^(-1))处理人体正常肝细胞(L02)24h后,细胞存活率仍高于83%,凋亡率仅为6.93%,表明香茅油纳米乳剂具有较低的细胞毒性。本研究有助于设计和构建稳定、高效、安全的农业纳米乳剂,同时为植物精油作为农业杀菌剂提供了切实可行的解决方案。

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.

Dispersion of exciton-polariton based on ZnO/MgZnO quantum wells at room temperature

We report observation of dispersion for coupled exciton-polariton in a plate microcavity combining with ZnO/MgZnO multi-quantum well (QW) at room temperature. Benefited from the large exciton binding energy and giant oscillator strength, the room-temperature Rabi splitting energy can be enhanced to be as large as 60 meV. The results of excitonic polariton dispersion can be well described using the coupling wave model. It is demonstrated that mode modification between polariton branches allowing, just by controlling the pumping location, to tune the photonic fraction in the different detuning can be investigated comprehensively. Our results present a direct observation of the exciton-polariton dispersions based on two-dimensional oxide semiconductor quantum wells, thus provide a feasible road for coupling of exciton with photon and pave the way for realizing novel polariton-type optoelectronic devices.

Biomarkers of aging

Aging biomarkers are a combination of biological parameters to(i)assess age-related changes,(ii)track the physiological aging process,and(iii)predict the transition into a pathological status.Although a broad spectrum of aging biomarkers has been developed,their potential uses and limitations remain poorly characterized.An immediate goal of biomarkers is to help us answer the following three fundamental questions in aging research:How old are we?Why do we get old?And how can we age slower?This review aims to address this need.Here,we summarize our current knowledge of biomarkers developed for cellular,organ,and organismal levels of aging,comprising six pillars:physiological characteristics,medical imaging,histological features,cellular alterations,molecular changes,and secretory factors.To fulfill all these requisites,we propose that aging biomarkers should qualify for being specific,systemic,and clinically relevant.

Inflammation,epigenetics,and metabolism converge to cell senescence and ageing:the regulation and intervention

Remarkable progress in ageing research has been achieved over the past decades.General perceptions and experimental evidence pinpoint that the decline of physical function often initiates by cell senescence and organ ageing.Epigenetic dynamics and immunometabolic reprogramming link to the alterations of cellular response to intrinsic and extrinsic stimuli,representing current hotspots as they not only(re-)shape the individual cell identity,but also involve in cell fate decision.This review focuses on the present findings and emerging concepts in epigenetic,inflammatory,and metabolic regulations and the consequences of the ageing process.Potential therapeutic interventions targeting cell senescence and regulatory mechanisms,using state-of-the-art techniques are also discussed.

Investigation of flow unsteadiness in a highly-loaded compressor cascade using a dynamic mode decomposition method

Unsteady flow in the hub endwall region has long been a hot topic in the turbomachinery community.However important it is to the performance of the whole engine,the coherent unsteady flow phenomena are still not well understood.In this paper,the complex flow field in the hub endwall of a cantilevered compressor cascade has been investigated through numerical approach.The predicted results were validated by experimental data.To highlight the dominant flow structures among irregular and chaotic motions of various vortices,a Dynamic Mode Decomposition(DMD)method was utilized.The results show that there exist three dominant periodic flow structures:the oscillation of the leakage vortex,a circumferential migration of a Breakdown Induced Vortex(BIV)and the fluctuation of the passage vortex.These three coherent structures all together form a self-sustained closed loop which accounts for the flow unsteadiness of the studied cascade.During this process,the BIV plays a key role in inducing the flow unsteadiness.Only if the BIV is strong enough to affect the passage vortex,the flow unsteadiness occurs.This study expands current knowledge base of flow unsteadiness in a compressor environment,and shows the efficacy of the DMD method for revealing the origin of flow unsteadiness.

Research progress on geosynchronous synthetic aperture radar

Based on its ability to obtain two-dimensional(2D)high-resolution images in all-time and all-weather conditions,spaceborne synthetic aperture radar(SAR)has become an important remote sensing technique and the study of such systems has entered a period of vigorous development.Advanced imaging modes such as radar interferometry,tomography,and multi-static imaging,have been demonstrated.However,current in-orbit spaceborne SARs,which all operate in low Earth orbits,have relatively long revisit times ranging from several days to dozens of days,restricting their temporal sampling rate.Geosynchronous SAR(GEO SAR)is an active research area because it provides significant new capability,especially its much-improved temporal sampling.This paper reviews the research progress of GEO SAR technologies in detail.Two typical orbit schemes are presented,followed by the corresponding key issues,including system design,echo focusing,main disturbance factors,repeat-track interferometry,etc,inherent to these schemes.Both analysis and solution research of the above key issues are described.GEO SAR concepts involving multiple platforms are described,including the GEO SAR constellation,GEO-LEO/airborne/unmanned aerial vehicle bistatic SAR,and formation flying GEO SAR(FF-GEO SAR).Due to the high potential of FF-GEO SAR for three-dimensional(3D)deformation retrieval and coherence-based SAR tomography(TomoSAR),we have recently carried out some research related to FF-GEO SAR.This research,which is also discussed in this paper,includes developing a formation design method and an improved TomoSAR processing algorithm.It is found that GEO SAR will continue to be an active topic in the aspect of data processing and multi-platform concept in the near future.

Inflamm-aging of hematopoietic stem cells

Hematopoietic stem cells(HSCs)are responsible for generating all blood cells throughout life.Apart from the role of HSCs in maintaining the homeostasis of blood cell production process,they must respond quickly to hematopoietic challenges,such as infection or blood loss.HSCs can be directly/indirectly activated and engage in blood formation for the acute needs in response to inflammation.Recent findings highlight the emerging role of inflammation signaling on HSC fate decision and shaping the hematopoietic system during aging.Here,we summarize recent studies identifying the changes in inflammation and their role in modulation of HSC function and discuss the interaction between inflammation and HSC biology in the contexts of aging and hematological malignancy.