Effects of zinc on χ-Fe_(5)C_(2) for carbon dioxide hydrogenation to olefins:Insights from experimental and density function theory calculations

Production of light olefins from CO_(2), the primary greenhouse gases, is of great importance to mitigate the adverse effects of CO_(2) emission on environment and to supply the value-added products from nonpetroleum resource. However, development of robust catalyst with controllable selectivity and stability remains a challenge. Herein, we report that Zn-promoted Fe catalyst can boost the stable and selective production of light olefins from CO_(2). Specifically, the Zn-promoted Fe exhibits a highly stable activity and olefin selectivity over 200 h time-on-stream compared to the unpromoted Fe catalyst, primarily owing to the preservation of active χ-Fe_(5)C_(2) phase. Structural characterizations of the spent catalysts suggest that Zn substantially regulates the content of iron carbide on the surface and suppresses the reoxidation of bulk iron carbide during the reaction. DFT calculations confirm that adsorption of surface carbon atoms and graphene-like carbonaceous species are not thermochemically favored on Zn-promoted Fe catalyst. Carbon deposition by CAC coupling reactions of two surface carbon atoms and dehydrogenation of CH intermediate are also inhibited. Furthermore, the effects of Zn on antioxidation of iron carbide were also investigated. Zn favored the hydrogenation of surface adsorbed oxygen atoms to H_(2)O and the desorption of H_(2)O, which reduces the possibility of surface carbide being oxidized by the chemisorbed oxygen.

Simulation Modelling and Techno-Economics of Supercritical Carbon Dioxide Recompression Closed Brayton Cycle

In recent years, there has been global interest in meeting targets relating to energy affordability and security while taking into account greenhouse gas emissions. This has heightened major interest in potential investigations into the use of supercritical carbon dioxide (sCO2) power cycles. Climate change mitigation is the ultimate driver for this increased interest;other relevant issues include the potential for high cycle efficiency and a circular economy. In this study, a 25 MWe recompression closed Brayton cycle (RCBC) has been assessed, and sCO2 has been proposed as the working fluid for the power plant. The methodology used in this research work comprises thermodynamic and techno-economic analysis for the prospective commercialization of this sCO2 power cycle. An evaluated estimation of capital expenditure, operational expenditure, and cost of electricity has been considered in this study. The ASPEN Plus simulation results have been compared with theoretical and mathematical calculations to assess the performance of the compressors, turbine, and heat exchangers. The results thus reveal that the cycle efficiency for this prospective sCO2 recompression closed Brayton cycle increases (39% - 53.6%) as the temperature progressively increases from 550˚C to 900˚C. Data from the Aspen simulation model was used to aid the cost function calculations to estimate the total capital investment cost of the plant. Also, the techno-economic results have shown less cost for purchasing equipment due to fewer components being required for the cycle configuration as compared to the conventional steam power plant.

Effects of Selenium Dioxide on Apoptosis, Bcl-2 and P53 Expression, Intracellular Reactive Oxygen Species and Calcium Level in Three Human Lung Cancer Cell Lines

Objective: To evaluate the anti-tumor effects of SeO2 and its mechanisms on three human lung cancer cell lines. Methods: Three lung cancer cells A549, GLC-82 and PG were treated with 3-30 μmol/L SeO2. Flow cytometry was used to detect apoptosis, and analyze the changes of expression of p53 and Bcl-2, as well as ROS and Ca2+ level within cells. Results:SeO2 markedly inhibited cell proliferation and viability, and prompted apoptosis after 48 h treatment. SeO2 at 10 μmol/L induced 47.8% apoptosis in A549 cells, 40.8% in GLC-82 cells, 18.2% in PG cells. SeO2 at 30 μmol/L induced 37.8% apoposis in PG cells,but did not increase apoptotic raes in other two cells. SeO2 could down-regulate the mean fluorescent intensity of Bcl-2 from 65.8 to 9.6 in A549, but not in GLC-82 and in PG cells, up-regulate wild type p53 level in all three cells. SeO2 decreased the ROS and Ca2+ level markedly within three tested cells. Conclusion: SeO2 showed anti-tumor effect via apoptosis pathway in three lung cancer cell lines. The decrease of ROS and Ca2+ level within cells as well as regulation of Bcl-2 and p53 expression may play important roles in above apoptotic procedure.

CeO_(2)改性CuO纳米棒协同促进电催化还原CO_(2)制乙烯

随着社会经济发展及人类活动扩大,大气中CO_(2)的浓度日益增加,且带来诸多环境污染问题.因此开发高效、可持续的CO_(2)转化方法至关重要.本文基于电催化反应机理,制备了一系列CuO/CeO_(2)纳米棒复合材料,以促进二氧化碳高选择性还原为C2H_(4).结果表明,经过优化后的CuO/CeO_(2)-2(molCeO_(2):mol_(CuO)=2%)电催化剂在电流密度达到20mA/cm^(2)时,所需电位最低(-0.99V vs.RHE),且对乙烯具有最高的选择性,在电压为-1.08V vs.RHE时,法拉第效率高达46%.此优势可能与大的表面积、更粗糙的表面以及CuO和CeO_(2)之间的协同效应有关,有效提高了反应活性位点和电子转移效率.本研究将为设计和优化CuO基复合材料以实现CO_(2)的高效转化提供理论指导.

SCCO_(2)作用下不同含水性煤孔裂隙结构变化机制

深部煤层封存CO_(2)增产CH_(4)产出过程中,处于超临界状态的CO_(2)(SCCO_(2))与煤中矿物质发生反应,改变煤的孔隙性,进而影响煤层封存CO_(2)的效果和甲烷增产效果。为发现SCCO_(2)–H_(2)O–煤岩作用对煤中孔隙的影响特征,以焦煤为研究对象,开展了不同含水条件下的超临界CO_(2)改造煤实验,基于矿物组成和孔隙性测定结果,对比煤中主要矿物质和不同尺度的孔裂隙变化的差异,探讨了不同含水状态下SCCO_(2)流体对孔裂隙性的作用机制。研究表明:①SCCO_(2)作用后,煤体表面粗糙、疏松,且由于矿物溶蚀使得一些裂隙得到贯通,微裂隙连通性增强。②SCCO_(2)流体对煤具有“扩孔”作用,表现为微、小孔含量下降,中、大孔占比升高,也即微、小孔隙向大孔隙的转化,且孔隙连通性改善;进一步发现,萃余煤吸附孔的分形维数稍微增加,粗糙度增大,而渗流孔的分形维数显著降低,复杂性和非均质性降低。③SCCO_(2)对煤中碳酸盐类矿物的溶解性最好,其次是黏土矿物,且随着含水率增加,萃余煤中的碳酸盐矿物占比先增加后减小。SCCO_(2)使干燥基态、饱和水态煤样中碳酸盐矿物显著溶解,有效改善了孔隙结构,且对饱和水态煤样作用效果更好。空气干燥基态煤样经SCCO_(2)作用后,新生成的白云石矿物聚集在孔喉中造成堵孔效应,缩小原有大孔隙尺寸,是引起不同含水性煤孔隙差异性变化的主要原因。

Regeneration of 2-amino-2-methyl-1-propanol used for carbon dioxide absorption

To improve the efficiency of the carbon dioxide cycling process and to reduce the regeneration energy consumption, a sterically hindered amine of 2-amino-2-methyl-1- propranol （AMP） was investigated to determine its regeneration behavior as a CO2 absorbent. The CO2 absorption and amine regeneration characteristics were experimentally examined under various operating conditions. The regeneration efficiency increased from 86.2% to 98.3% during the temperature range of 358 to 403 K. The most suitable regeneration temperature for AMP was 383 K, in this experiment condition, and the regeneration efficiency of absorption/regeneration runs descended from 98.3% to 94.0%. A number of heat-stable salts （HSS） could cause a reduction in CO2 absorption capacity and regeneration efficiency. The results indicated that aqueous AMP was easier to regenerate with less loss of absorption capacity than other amines, such as, monoethanolamine （MEA）, diethanolamine （DEA）, diethylenetriamine （DETA）, and N-methyldiethanolamine （MDEA）.

Defect engineering of high-loading single-atom catalysts for electrochemical carbon dioxide reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides an attractive approach to carbon capture and utilization for the production high-value-added products.However,CO_(2)RR still suffers from poor selectivity and low current density due to its sluggish kinetics and multitudinous reaction pathways.Single-atom catalysts(SACs)demonstrate outstanding activity,excellent selectivity,and remarkable atom utilization efficiency,which give impetus to the search for electrocatalytic processes aiming at high selectivity.There appears significant activity in the development of efficient SACs for CO_(2)RR,while the density of the atomic sites remains a considerable barrier to be overcome.To construct high-metal-loading SACs,aggregation must be prevented,and thus novel strategies are required.The key to creating high-density atomically dispersed sites is designing enough anchoring sites,normally defects,to stabilize the highly mobile separated metal atoms.In this review,we summarized the advances in developing high-loading SACs through defect engineering,with a focus on the synthesis strategies to achieve high atomic site loading.Finally,the future opportunities and challenges for CO_(2)RR in the area of high-loading single-atom electrocatalysts are also discussed.

具有增强光催化和抗菌活性的TiO_(2)@Ag-GO复合材料

光催化降解环境中的污染物被认为一种理想的清洁方法,其中二氧化钛(TiO_(2))是目前最有前途的光催化材料之一。但由于能带宽、光生电子与空穴快速复合等特点,限制了其利用效率和范围,开发一种高效的TiO_(2)基光催化复合材料具有重要意义。通过简单的溶胶-凝胶法和一步Marangoni法,将TiO_(2)和Ag纳米颗粒(AgNPs)和氧化石墨烯(GO)有效结合,制备出显著增强光催化活性和抗菌能力的复合材料TiO_(2)@Ag-GO。氧化石墨烯(GO)具有多个催化活性中心,可以高效地进行光催化反应降解污染物。同时,还能提高电荷分离程度,抑制光生电子和空穴复合,提高TiO_(2)光催化活性。AgNPs具有存储电子和促进电荷分离的能力,同时释放的Ag+,赋予材料广谱的抗菌性能。光催化试验抑菌试验结果表明,复合材料能高效降解亚甲基蓝染料,2 h降解率达到74.5%,同时对金黄色葡萄球菌和铜绿杆菌有较强的杀灭作用。这种简易制备的高催化和杀菌功能的TiO_(2)基复合材料在光催化清洁领域有很大的应用潜力。

Photocatalytic reduction of carbon dioxide to methanol by Cu_2O/SiC nanocrystallite under visible light irradiation

The Cu2O/SiC photocatalyst was obtained from SiC nanoparticles （NPs） modified by Cu2O. Their photocatalytic activities for reducing CO2 to CH3OH under visible light irradiation have been investigated. The results indicated that besides a small quantity of 6H-SiC, SiC NPs mainly consisted of 3C-SiC. The band gaps of SiC and Cu2O were estimated to be about 1.95 and 2.23 eV from UV-Vis spectra, respectively. The Cu2O modification can enhance the photocatalytic performance of SiC NPs, and the largest yields of methanol on SiC, Cu2O and Cu2O/SiC photocatalysts under visible light irradiation were 153, 104 and 191μmol/g, respectively.

Cu/TiO_(2) Photocatalysts for CO_(2) Reduction: Structure and Evolution of the Cocatalyst Active Form

Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.

Surface Acidity/Basicity and Catalytic Reactivity of CeO2/7-Al2O3 Catalysts for the Oxidative Dehydrogenation of Ethane with Carbon Dioxide to Ethylene

Dehydrogenation of ethane to ethylene in CO_2 was investigated overCeO_2/γ-Al_2O_3 catalysts at 700℃ in a conventional flow reactor operating at atmosphericpressure. XRD, BET and microcalori-metric adsorption techniques were used to characterize thestructure and surface acidity/basicity of the CeO_2/γ-Al_2O_3 catalysts. The results show that thesurface acidity decreased while the surface basicity increased after the addition of CeO_2 toγ-Al_2O_3. Accordingly, the activity of the hydrogenation reaction of CO_2 increased, which mightbe responsible for the enhanced conversion in the dehydrogenation of ethane to ethylene. The highestethane conversion obtained was about 15% for the 25%CeO_2/γ-Al_2O_3. The selectivity to ethylenewas high for all the CeO_2, γ-Al_2O_3 and CeO2/γ-Al_2O_3 catalysts.

Porous metal oxides in the role of electrochemical CO_(2) reduction reaction

The global energy-related CO_(2) emissions have rapidly increased as the world economy heavily relied on fossil fuels.This paper explores the pressing challenge of CO_(2) emissions and highlights the role of porous metal oxide materials in the electrocatalytic reduction of CO_(2)(CO_(2)RR).The focus is on the development of robust and selective catalysts,particularly metal and metal-oxide-based materials.Porous metal oxides offer high surface area,enhancing the accessibility to active sites and improving reaction kinetics.The tunability of these materials allows for tailored catalytic behavior,targeting optimized reaction mechanisms for CO_(2)RR.The work also discusses the various synthesis strategies and identifies key structural and compositional features,addressing challenges like high overpotential,poor selectivity,and low stability.Based on these insights,we suggest avenues for future research on porous metal oxide materials for electrochemical CO_(2) reduction.

Morphology Controlling of the Ultrafine Cerium Dioxide (CeO_2) Precursor

The synthesis of ultrafine cerium dioxide precursor via homogeneous precipitation was studied. Mixed aqueous solution of anhydrous cerium nitrate and urea was first heated to 85℃ for 2 h, and the prepared suspension was then aged at room temperature for various periods of time. White precipitate was finally collected by centrifuging and washed with distilled water and anhydrous ethanol. The obtained cerium dioxide (CeO2) precursor was observed with SEM. It was found that the morphology and size of the precursor were strongly affected by aging time and stirring conditions (with or without stirring). The precipitated fine spherical particles of the precursor changed their shape from ellipse to slice or directly to slice. Fine spherical monodispersed (300 nm) precursor powders could be obtained by controlling the aging time. Stirring the solution also could change the reaction process and thus the morphology and size of the precursor were changed.

Effects of Ce/Zr ratio on the structure and performances of Co-Ce_(1-x)Zr_xO_2 catalysts for carbon dioxide reforming of methane

The Co-incorporated Ce1-xZrxO2 catalysts were prepared by co-precipitation for carbon dioxide reforming of methane.The ratio of Ce to Zr was varied to optimize the performances of co-precipitated Co-Ce-Zr-Ox catalysts.The prepared catalysts were characterized by various physico-chemical characterization techniques including TPR,X-ray diffraction,N2 adsorption at low temperature,XPS and CO2-TPSR.The co-precipitated Co-Ce0.8Zr0.2O2 sample containing 16% CoO exhibited a higher catalytic activity among the five catalysts,and the activity was maintained without significant loss during the reaction for 60 h.Under the conditions of 750 ℃,0.1 MPa,36000 ml/（h gcat）,and CO2/CH4 molar ratio of 1：1,the CO2 conversion over this catalyst was 75% while the CH4 conversion was 67%.The cubic Ce0.8Zr0.2O2 facilitated a higher dispersion and a higher reducibility of the cobalt component,and the apparent activation energy for Co-Ce0.8Zr0.2O2 sample was 49.1 kJ/mol in the CO2/CH4 reforming reaction.As a result,the Co-Ce0.8Zr0.2O2 sample exhibited a higher activity and stability for the reforming of CH4 with CO2.

合成气/CO_(2)火焰传播过程中辐射再吸收的影响

针对生物质制取合成气燃料制备和应用过程中CO_(2)掺混的影响,对合成气/空气/CO_(2)预混火焰中开展数值模拟,通过不同的辐射模型研究辐射再吸收对火焰传播速度的影响。结果表明,辐射再吸收提高了火焰传播速度,最大提升幅度可达11.15%。随当量比增加,辐射再吸收对火焰传播速度的提升幅度从11.15%减小至3.12%,受预热导致的化学效应控制。H自由基在贫燃工况占据主导地位,辐射再吸收通过反应H+O_(2)==O+OH影响火焰传播速度;而富燃工况下,与OH自由基相关的反应H+OH+M=H_(2)O+M是辐射再吸收影响火焰传播速度的主导反应。

Screening of MgO- and CeO_2-Based Catalysts for Carbon Dioxide Oxidative Coupling of Methane to C_(2+) Hydrocarbons

The catalyst screening tests for carbon dioxide oxidative coupling of methane (CO2-OCM) have been investigated over ternary and binary metal oxide catalysts. The catalysts are prepared by doping MgO- and CeO2-based solids with oxides from alkali (Li2O), alkaline earth (CaO), and transition metal groups (WO3 or MnO). The presence of the peroxide (O2-2) active sites on the Li2O2, revealed by Raman spectroscopy, may be the key factor in the enhanced performance of some of the Li2O/MgO catalysts. The high reducibility of the CeO2 catalyst, an important factor in the CO2-OCM catalyst activity, may be enhanced by the presence of manganese oxide species. The manganese oxide species increases oxygen mobility and oxygen vacancies in the CeO2 catalyst. Raman and Fourier Transform Infra Red (FT-IR) spectroscopies revealed the presence of lattice vibrations of metal-oxygen bondings and active sites in which the peaks corresponding to the bulk crystalline structures of Li2O, CaO, WO3 and MnO are detected. The performance of 5%MnO/15%CaO/CeO2 catalyst is the most potential among the CeO2-based catalysts, although lower than the 2%Li2O/MgO catalyst. The 2%Li2O/MgO catalyst showed the most promising C2+ hydrocarbons selectivity and yield at 98.0% and 5.7%, respectively.

A Multilayer Study of pCO2 in the Surface Waters of the Yellow and South China Seas in Spring and the Sea-Air Carbon Dioxide Flux

A multilayer study of pCO2 for the Yellow and South China Seas in the surface waters was conducted based on data from four cruises sponsored by the China SOLAS Project in 2005 and 2006,including data for the surface microlayer(SML) ,subsurface layer(SSL) and surface layer(SL) . The carbon fluxes across the air-sea interface were calculated. The results showed that the pCO2 values in the surface waters of the study area decreased in the following order:pCO2 SML> pCO2 SSL> pCO2 SL. The highest values were found in March for all SML,SSL and SL,followed by those in April,and the lowest were in May. The pCO2 values had a significant positive correlation with temperature or salinity. While there was no relationship between pCO2 and longitude,there was a significant negative correlation between it and latitude,i.e.,'high latitude low pCO2'. By using four calculation models,the carbon dioxide fluxes(FC O2) in spring in the Yellow and South China Seas,which were found to act as a 'sink' of atmospheric CO2,were preliminarily estimated on the basis of the pCO2 data in the SML to be -7.00×106 t C and -22.35×106 t C,respectively. It is suggested that the FC O2calculated on the basis of pCO2 data in the SML is more reliable than that calculated on the basis of those in the SL.

Well-dispersed SnO2 nanocrystals on N-doped carbon nanowires as efficient electrocatalysts for carbon dioxide reduction

The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.

Kinetics of Reactive Extraction of Nd from Nd2O3 with TBP-HNO3 Complex in Supercritical Carbon Dioxide

The process based on supercritical fluid extraction for reprocessing of the spent nuclear fuel has some remarkable advantages over the plutonium-uranium extraction(PUREX) process.Especially,it can minimize the generation of secondary waste.Dynamic reactive extraction of neodymium oxide(Nd2O3) in supercritical carbon dioxide(SC-CO2) containing tri-n-butyl phosphate-nitric acid(TBP-HNO3) complex was investigated.Temperature showed a positive effect on the extraction efficiency,while pressure showed a negative effect when the unsaturated TBP-HNO3 complex was employed for the dynamic reactive extraction of Nd2O3 in SC-CO2.Both temperature and pressure effects indicated that the kinetic process of the reactive extraction was controlled by the chemical reaction.A kinetic model was proposed to describe the extraction process.

CO_(2)驱分层注气工艺管柱适用性分析及展望

目前,我国现场应用的注气管柱多为笼统注气管柱、同心双管分层注气管柱及偏心投捞分层注气管柱,该类管柱存在着分层数受限、测调效率低、测调精度差及适应性差等问题,难以满足CO_(2)驱油田的精细、高效开发需求。针对这一现象,在现有成熟分层注水管柱的基础上,设计了液控分层注气管柱、测调一体分层注气管柱、有缆智能分层注气管柱,并对这3种分层注气管柱进行了技术适应性分析和实施难点分析,分析发现:所设计的3种分层注气管柱各有优势,配套井下气体流量计的研制既是设计管柱的主要实施难点也是实现精细化注气的关键。最后,对各类流量测量技术进行了技术特性及研究难度分析,并对井下气体流量计的设计选型提出了建议和展望。