Sub-2 nm mixed metal oxide for electrochemical reduction of carbon dioxide to carbon monoxide

Mixed metal oxide(MMO) represents a critical class of materials that can allow for obtaining a dynamic interface between its components:reduced metal and its metal oxide counterpart during an electrocatalytic reaction.Here,a synthetic method utilizing a MOF-derived micro/mesoporous carbon as a template to prepare sub-2 nm MMO catalysts for CO_(2) electro reduction is reported.Starting from the zeolite imidazolate framework(ZIF-8),the pyrolyzed derivatives were used to synthesize sub-2 nm Pd-Ni MMO with different compositions.The Ni-rich(Pd_(20)-Ni_(80)/ZC) catalyst exhibits unexpectedly superior performance for CO production with an improved Faradaic efficiency(FE) of 95.3% at the current density of 200 mA cm^(-2) at-0.56 V vs.reversible hydrogen electrode(RHE) compared to other Pd-Ni compositions.X-ray photoelectron spectroscopy(XPS) analysis confirms the presence of Ni^(2+) and Pd^(2+) in all compositions,demonstrating the presence of MMO.Density functional theory(DFT) calculation reveals that the lower CO binding energy on the surface of the Pd_(20)-Ni_(80) cluster eases CO desorption,thus increasing its production.This work provides a general synthetic strategy for MMO electrocatalysts and can pave a new way for screening multimetallic catalysts with a dynamic electrochemical interface.

Nitrogen Dioxide, Carbon Monoxide, Natural and Anthropomorphic Effects, and Earth’s Changing Climate

This study will both compare and contrast the characteristics and roles of two pollutants: nitrogen dioxide and carbon monoxide. It will begin by tracing each gas’ negative contributions to the Earth’s spheres, as well as relate any negative links that each plays concerning human activity, health, and interaction with the environment. It will include an in-depth analysis of what the proliferation of such toxic gases indicates about human production and causality, plus reflect on any current attempts being made to improve the effects of these pollutants on the environment. This examination will also inspect three NASA missions, i.e., MOPITT/Terra, AIRS/Aqua, and OMI/Aura, the aim of which, among many other tasks, is to detect pollutants within the Earth’s various spheres, as well as analyze weather anomalies, improve prediction methodology, and chronicle meteorological patterns for future study. It will also cover some of the goals, engineering breakthroughs, and in one case, the limitations, of these three satellite missions. Finally, it should be noted that in all stages of this discussion, the author’s main aim will be to focus on the positives that need to be implemented in order to improve the current situations that both anthropogenic and natural disasters have created for the planet.

Recovery of carbon monoxide from flue gases by reactive absorption in ionic liquid imidazolium chlorocuprate(I): Mass transfer coefficients

Recovery of carbon monoxide from flue gases by selective absorption of carbon monoxide in an imidazolium chlorocuprate（l） ionic liquid is considered in this work as an alternative to the use of molecular volatile solvents such as aromatic hydrocarbons. The present work evaluates the CO mass transfer rates from the gas phase to the ionic liquid solutions in the absence of chemical reaction. To that end, carbon dioxide was employed as an inert model gas and absorption experiments were performed to assess the influence of different process variables in a batch reactor with fiat gas-liquid interface. The experimental mass transfer coefficients showed significant var- iation with temperature, （3.4-10.9） × 10^-7 m·s^-1 between 293 and 313 K; stirring speed, （10.2- 33.1）× 10^-7 m.s 1 between 100 and 300 r·min^-1; and concentration of copper（1）, （6.6-10.2） × 10^-7 m·s^-1 between 0.25 and 2 mol· L^- 1. In addition, the mass transfer coefficients were eventually found to follow a poten- tial proportionality of the type kL ∝μ^-0.5 and the dimensionless correlation that makes the estimation of the mass transfer coefficients possible in the studied range of process variables was obtained： Sh=10^-2.64 Re^1.07 , Sc^0.75,These results constitute the first step in the kinetic analysis of the reaction between CO and imidazolium chlorocuprate（I） ionic liquid that determines the design of the separation units.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Photopromoted Carbonylation of Alkyl Bromides Catalyzed by Copper Salts under Ambient Conditions

Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.

Single atom Cu-N-C catalysts for the electro-reduction of CO_(2) to CO assessed by rotating ring-disc electrode

The electrochemical CO_(2) reduction reaction(CO_(2)RR) to controllable chemicals is considered as a promising pathway to store intermittent renewable energy. Herein, a set of catalysts based on copper-nitrogendoped carbon xerogel(Cu-N-C) are successfully developed varying the copper amount and the nature of the copper precursor, for the efficient CO_(2)RR. The electrocatalytic performance of Cu-N-C materials is assessed by a rotating ring-disc electrode(RRDE), technique still rarely explored for CO_(2)RR. For comparison, products are also characterized by online gas chromatography in a H-cell. The as-synthesized Cu-NC catalysts are found to be active and highly CO selective at low overpotentials(from -0.6 to -0.8 V vs.RHE) in 0.1 M KHCO_(3), while H_(2) from the competitive water reduction appears at larger overpotentials(-0.9 V vs. RHE). The optimum copper acetate-derived catalyst containing Cu-N_(4) moieties exhibits a CO_(2)-to-CO turnover frequency of 997 h^(-1) at -0.9 V vs. RHE with a H_(2)/CO ratio of 1.8. These results demonstrate that RRDE configuration can be used as a feasible approach for identifying electrolysis products from CO_(2)RR.

Effect of La_2O_3on Methanation of CO and CO_2over Ni-Mo/γ-Al_2O_3Catalyst

A series of Ni-Mo/-A12O3 methanation catalysts containing La2O3 were prepared by impregnation. The activities of catalysts for CO and CO2 methanation were investigated. The surface properties of the catalysts were studied by TEM, XPS and chemisorption of CO. The experimental results show that the addition of La2O3 increases the activities for the methanation of CO and CO2, the dispersity of nickel on catalysts, the active nickel surface area and the concentration of nickel atoms on the surface of Ni-Mo/-Al2O3 catalysts. At the same time, it also decreases the binding energy of Ni2p,. in catalysts.

CNT modified by mesoporous carbon anchored by Ni nanoparticles for CO_(2) electrochemical reduction

The design of novel catalysts for efficient electroreduction of CO_(2) into valueadded chemicals is a promising approach to alleviate the energy crisis.Herein,we successfully modify the carbon nanotube by a layer of mesoporous carbon shell anchored by nickel(Ni)nanoparticles.Ni species effectively enable carbon deposition derived from pyrolysis of surfactant 1-hexadecyl trimethyl ammonium bromide to form a mesoporous carbon shell.At the same time,Ni nanoparticles can be embedded in the mesoporous carbon shell due to the confinement effect.Owing to the dispersive Ni nanoparticles and N-doping active sites of mesoporous carbon,the as-prepared electrocatalyst exhibits exciting catalytic performance for the selective reduction of CO_(2) to carbon monoxide(CO)with a maximum Faradaic efficiency of 98%at a moderate overpotential of−0.81 V(vs.reversible hydrogen electrode)and a high partial current density of 60 mA cm^(−2) in H-cell with an aqueous electrolyte.

A DFT+U study of the structures and reactivities of polar CeO_2(100) surfaces

Density functional theory calculations corrected by on-site Coulomb interactions were carried out o study the structures of polar CeO2 （100） surfaces as well as activities during catalytic CO oxidation. The stabilities of various CeO2 （100） termination structures are discussed, and calculated energetics are presented. The most stable Ce〇2 （100） surface was obtained by removing half the outermost full layer of oxygen and the surface stability was found to decrease as the exposed oxygen concentration was increased. Assessing the reaction pathways leading to different final products during CO oxidation over the most stable CeO2 （100） surface, we determined that the formation of carbonate species competed with CO2 desorption. However, during CO oxidation on the less stable CeO2 （100） surfaces having more exposed oxygen, the CO is evidently able to react with surface oxygen, leading to CO2 formation and desorption. The calculation results and electronic analyses reported herein also indicate that the characteristic Ce 4/ orbitals are directly involved in deter-mining the surface stabilities and reactivities.

Effects of CO2-water interaction with coal on mineral content and pore characteristics

There are a large number of abandoned coalmines in China,and most of them are located around major coal-fired power stations,which are the largest emission sources of carbon dioxide(CO2).Considering the injection of CO2 into abandoned coalmines,which are usually in the flooded condition,it is necessary to investigate the effect of CO2-water-coal interaction on minerals and pore structures at different pressures,temperatures and times.It reveals that the CO2-water-coal interaction can significantly improve the solubility of Ca,S,Mg,K,Si,Al,Fe and Na.By comparing the mineral content and pore structure before and after CO2-water-coal interaction,quartz and kaolinite were found to be the main secondary minerals,which increased in all samples.The structures of micropores and mesopores in the range of 1.5-8 nm were changed obviously.Specific surface areas and pore volumes first increased and then decreased with pressure and time,while both increased with temperature.By using the Frenkel-Halsey-Hill model,the fractal dimensions of all samples were analyzed based on D(s1)and D(s2),which reflected the co mplexities of the pore surface and pore volume,respectively.The re sults show that fractal dimensions had very weak positive correlations with the carbon content.D(s1)had a positive correlation with the quartz and kaolinite contents,while D(s2)had a negative correlation with the quartz and kaolinite contents.

European legal framework related to underground mining and tunnelling concerning commission directive (EU) 2017/164, 31 January establishing a fourth list of indicative occupational exposure limit values

Directive(EU)2017/164 establishes a fourth list of indicative occupational exposure limit values(IOELVs)to protect workers from risks of exposure to hazardous chemicals.It states that in underground mining and tunnelling,Member States may benefit from a transitional period regarding IOELVs for nitrogen monoxide,nitrogen dioxide,and carbon monoxide,during which the existing established IOELVs may be applied.The European Advisory Committee on Health and Safety at Work questions the technical feasibility of the proposed IOELVs in underground mining(CO,NO and NO2)and tunnelling(NO and NO2).Challenges arise concerning the availability of measurement methodologies for compliance with proposed IOELVs(NO2)in underground mining and tunnelling environments.

Co-thermal in-situ reduction of inorganic carbonates to reduce carbon-dioxide emission

Thermal decomposition of inorganic metal carbonates is the main path to prepare metal oxides;nonetheless,it is always accompanied by the emission of large amounts of CO_(2) as one of the gas products.This study reports a concept of co-thermal insitu reduction of inorganic carbonates by using the energy released by carbonate decomposition under pure hydrogen atmosphere,which reduces the decarboxylation temperature and significantly inhibits the CO_(2) emissions.A combination of hydrogen–deuterium exchange,isotope experiment,and density functional theory calculations demonstrates that the CO results from the selective cleavage of Ca–O bonds at the surface of CaCO_(3) via the direct hydrogenation mechanism at relatively low temperature.However,it undergoes the reverse water–gas shift reaction path at high temperature,i.e.,CO being produced by the reduction of CO_(2) released by the decomposition of carbonates.This study sheds light on the potential of green hydrogen technology for inorganic carbonate valorization toward high value-added products,which can facilitate the large-scale industrial applications.

Influence of Ionization Degrees on Conversion of CO and CO_2 in Atmospheric Plasma near the Ground

A zero-dimensional model is used to study the processes of physical and chemical reactions in atmospheric plasma with different ionization degrees near the ground （0 km）. The temporal evolutions of CO, C02 and other main reactants （namely OH and O2）, which affect the conversion of CO and C02, are obtained for afterglow plasma with different initial values. The results show that the consumption rate of CO is largest when the initiM electron number density neo=1012 cm-3, i.e. the ionization degree is 0.000004%. The number density of CO2 is relatively small when neo=1016 cm-3, i.e. the ionization degree is 0.04%, whereas they are very close under the condition of other ionization degrees. Considering the total number densities of CO and C02 and the consumption rate of CO comprehensively, the best condition is neo=1013 cm-3, i.e. the ionization degree is 0.00004% for reducing the densities of CO and CO2 in the atmospheric plasma. The temporal evolutions of N＋, Ar＋, CO＋ and CO＋ are also shown, and the influences on the temporal evolutions of CO and C02 are analyzed with increasing ionization degree.

Effect of CO_(2) Curing on the Physical Properties of Recycled Coarse Aggregate with Different Attached Mortar Contents

The effects of carbon dioxide (CO_(2)) curing conditions (temperature,relative humidity and CO_(2) curing time) on the physical properties of recycled coarse aggregate (RCA) with varying attached mortar (AM) contents were studied.Before and after CO_(2) curing,the physical properties in terms of the apparent density,water absorption and crushing value of RCA were tested and the quality of RCA was determined.Besides,scanning electron microscope was used to observe the microstructure of RCA.Results show that the physical properties variation of RCA with higher AM content are more significant,and the quality of RCA with lower AM content is easier to be upgraded during CO_(2) curing.The physical properties of RCA with 40.8% AM content are earlier stable than that with no less than 44.5% AM content during CO_(2) curing.The optimal temperature and relative humidity are 50 ℃ and 55% for CO_(2) curing,respectively.CO_(2) curing is incapable of upgrading the quality of RCA with AM no less than 50.6%.The quality of RCA with 44.5% AM content can be upgraded only under the optimum CO_(2) curing conditions.Under relative humidity higher than 40% and the CO_(2) curing time more than 12 h,CO_(2) curing upgrades the quality of RCA with 40.8% AM content.

Formation and removal of active oxygen species for the non-catalytic CO oxidation on Au/TiO_2 catalysts

Applying quantitative temporal analysis of products reactor measurements, we studied the reactive removal of active oxygen present on Au/TiO2 catalysts after calcination at elevated temperatures （400 ＆#176;C） by CO pulses and its replenishment by O2 pulses at 80 ＆#176;C, focusing on the nature of the active oxygen species. In contrast to previous studies, which mainly focused on and clarified the nature of the active oxygen species for the catalytic CO oxidation, which is reversibly formed and replenished under typical reaction conditions, this study demonstrates that directly after calcina‐tion an additional oxygen species is present. This species is also active for the CO oxidation, but it is not or only very little formed under typical reaction conditions. Implications of these results on the mechanistic understanding of the CO oxidation on Au/TiO2, in particular on the role of different active oxygen species, will be discussed.

Emission of Combustible Gases at Traffic and Practising Waste Dumpsite in Freetown, Sierra Leone: A Pilot Study

An assessment of the emission of combustible gases in developing countries requires reliable analytical realtime monitors that can rapidly screen them with minimal handling. Considering the expensive nature of monitoring environmental pollutants, chemical sensors are expected to play a pivotal role in measuring and recording environmental data. The Drager X am 5000 was used to report emission levels of combustible gases in this study, namely;nitrogen dioxide (NO2), sulphur dioxide (SO2) and carbon monoxide (CO) at traffic and practising waste dumpsite in Freetown, the main city of Sierra Leone. Hourly average values for the three pollutants were recorded in the morning, afternoon and evening periods, respectively. The range of values were 18 - 76 ppb for NO2, 211 - 506 ppb for SO2 and 11 - 14 ppm for CO at traffic site;and 6 - 16 ppb for NO2, 118 - 276 ppb for SO2 and 8 - 15 ppm for CO at the dumpsite, respectively. There were significantly high hourly variations for NO2 and SO2 at the traffic site and for CO and SO2 at the dumpsite. Evidence of peak values showed emission levels that were considered dangerous for human exposure. This pilot study revealed that combustible gases released in certain areas of the capital city are a concern for both public health officials and environmental advocates.

The Effect of the Hot Springs at the Umm Qeis Archaeological Site and Museum

Several recent studies have pointed out that northern parts of Jordan are exposed to high levels of the effect of the hot spring, which is widely known to have severe impacts on health, vegetation and structures. North Jordan has a wealth of ancient heritage including six out of the ten Decapolis Cities. Air pollution that comes out from the hot springs is alleged to deteriorate and erode buildings, structures, statues and monuments through acid deposition. Therefore, this research was conducted to assess air quality at Gadara, the capital of the ancient Decapolis and suggest mitigation measures that have to be adopted in order to save the ancient heritage against further deterioration. Measurements revealed that most criteria air pollutants including sulfur dioxide, nitrogen dioxide and carbon monoxide attain corresponding national ambient air quality standards. Atmospheric concentrations of NO are strongly linked to the amount of 03. Simultaneous exposure to SO2 and NO2 demonstrated that a catalytic reaction takes place which increases the rate of sulphate production after 30 h exposure.

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。

Al含量对含铝奥氏体不锈钢在高温超临界二氧化碳中均匀腐蚀性能的影响研究

为进一步提升奥氏体不锈钢作为超临界二氧化碳核反应堆候选包壳材料的耐腐蚀性能,对比研究了3种不同Al含量的含铝奥氏体不锈钢及不含Al基材在650℃/20 MPa的超临界二氧化碳环境中的均匀腐蚀行为。结果表明,材料的腐蚀增重随Al含量增加而降低,不同Al含量材料的腐蚀增重均近似服从抛物线生长规律。Al含量低于1.5wt%时,材料表面生成双层富Fe氧化膜,保护性差,渗碳层厚度可达约12μm;Al含量高于2.5wt%时,材料表面生成保护性氧化膜,外层富Cr、内层富Al,氧化膜及基体中仍存在渗碳行为,渗碳层厚度减小至约6μm。造成差异的原因是较高Al含量能有效促进保护性富Al氧化膜的形成,抑制Fe的向外扩散和C的向内扩散,进而提升材料的耐氧化和渗碳属性。

Catalytic reduction of SO_2 by CO over CeO_2-TiO_2 mixed oxides

The structure and catalytic desulfurization characteristics of CeO2-TiO2 mixed oxides were investigated by means ofX-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and catalytic activity tests. According to the results, a CeO2-TiO2solid solution is formed when the mole ratio of cerium to titanium n（Ce）：n（Ti） is 5：5 or greater, and the most suitable n（Ce）：n（Ti） isdetermined as 7：3, over which the conversion rate of SO2 and the yield of sulfur at 500℃ reach 93% and 99%, respectively.According to the activity testing curve, Ce0.7Ti0.3O2 （n（Ce）：n（Ti）=7：3） without any pretreatment can be gradually activated by reagentgas after about 10 min, and reaches a steady activation status 60 min later. The XPS results of Ce0.7Ti0.3O2 after different time ofSO2＋CO reaction show that CeO2 is the active component that offers the redox couple Ce4＋/Ce3＋ and the labile oxygen vacancies, andTiO2 only functions as a catalyst structure stabilizer during the catalytic reaction process. After 48 h of catalytic reaction at 500℃,Ce0.7Ti0.3O2 still maintains a stable structure without being vulcanized, demonstrating its good anti-sulfur poisoning performance.