Review of Iron-Based Catalysts for Carbon Dioxide Fischer-Tropsch Synthesis

Capturing and utilizing CO_(2)from the production process is the key to solving the excessive CO_(2)emission problem. CO_(2)hydrogenation with green hydrogen to produce olefins is an effective and promising way to utilize CO_(2)and produce valuable chemicals. The olefins can be produced by CO_(2)hydrogenation through two routes, i.e., CO_(2)-FTS (carbon dioxide Fischer- Tropsch synthesis) and MeOH (methanol-mediated), among which CO_(2)-FTS has significant advantages over MeOH in practical applications due to its relatively high CO_(2)conversion and low energy consumption potentials. However, the CO_(2)-FTS faces challenges of difficult CO_(2)activation and low olefins selectivity. Iron-based catalysts are promising for CO_(2)-FTS due to their dual functionality of catalyzing RWGS and CO-FTS reactions. This review summarizes the recent progress on iron-based catalysts for CO_(2)hydrogenation via the FTS route and analyzes the catalyst optimization from the perspectives of additives, active sites, and reaction mechanisms. Furthermore, we also outline principles and challenges for rational design of high-performance CO_(2)-FTS catalysts.

PdCu alloy anchored defective titania for photocatalytic conversion of carbon dioxide into methane with 100% selectivity

The photoreduction of CO_(2)into CH_(4)with simultaneous high activity and selectivity is a promising strategy to increase energy supply and alleviate global warming.However,the absence of the active sites that is responsible for the adsorption and activation of CO_(2)and the generation of CO and H2via side reactions often lead to poor efficiency and low selectivity of the catalyst.Herein,Cu,Pd,and PdCu metal clusters cocatalyst-anchored defective TiO_(2)nanotubes(Cu/TiO_(2)-SBO,Pd/TiO_(2)-SBO,and Pd1Cu1/TiO_(2)-SBO)were designed via a simple solution impregnation reduction and applied for photocatalytic conversion of CO_(2)to CH_(4).The Pd1Cu1/TiO_(2)-SBO photocatalyst exhibits excellent catalytic performance among the other catalysts for photoreduction of CO_(2)into CH_(4).More interestingly,the product selectivity of CH_(4)reaches up to 100%with a rate of 25μmol g^(-1)h^(-1).In-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and density functional theory(DFT)simulations indicate that the main reasons for the high selectivity of CH_(4)are attributed to the PdCu alloy and oxygen vacancies,which jointly enhance the photoinduced carrier separation and lower energy barriers of key intermediates.Moreover,due to the tunable d-band center of the Cu site in the PdCu alloy,the generated intermediates can be well prevented from poisoning and promoted to participate in further reactions.Hopefully,the current study will provide insight into the development of new,highly selective photocatalysts for the visible light-catalytic reduction of CO_(2)into CH_(4).

Potential evaluation of saline aquifers for the geological storage of carbon dioxide: A case study of saline aquifers in the Qian-5 member in northeastern Ordos Basin

The well-developed coal electricity generation and coal chemical industries have led to huge carbon dioxide(CO_(2))emissions in the northeastern Ordos Basin.The geological storage of CO_(2) in saline aquifers is an effective backup way to achieve carbon neutrality.In this case,the potential of saline aquifers for CO_(2) storage serves as a critical basis for subsequent geological storage project.This study calculated the technical control capacities of CO_(2) of the saline aquifers in the fifth member of the Shiqianfeng Formation(the Qian-5 member)based on the statistical analysis of the logging and the drilling and core data from more than 200 wells in the northeastern Ordos Basin,as well as the sedimentary facies,formation lithology,and saline aquifer development patterns of the Qian-5 member.The results show that(1)the reservoirs of saline aquifers in the Qian-5 member,which comprise distributary channel sand bodies of deltaic plains,feature low porosities and permeabilities;(2)The study area hosts three NNE-directed saline aquifer zones,where saline aquifers generally have a single-layer thickness of 3‒8 m and a cumulative thickness of 8‒24 m;(3)The saline aquifers of the Qian-5 member have a total technical control capacity of CO_(2) of 119.25×10^(6) t.With the largest scale and the highest technical control capacity(accounting for 61%of the total technical control capacity),the Jinjie-Yulin saline aquifer zone is an important prospect area for the geological storage of CO_(2) in the saline aquifers of the Qian-5 member in the study area.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Insights into carbon dioxide sequestration into coal seams through coupled gas flow-adsorption-deformation modelling

Injecting carbon dioxide(CO_(2))into coal seams may unlock substantial carbon sequestration potential.Since the coal acts like a carbon filter,it can preferentially absorb significant amounts of CO_(2).To explore this further,desorption of the adsorbed gas due to pressure drop is investigated in this paper,to achieve an improved understanding of the long-term fate of injected CO_(2) during post-injection period.This paper presents a dual porosity model coupling gas flow,adsorption and geomechanics for studying coupled processes and effectiveness of CO_(2) sequestration in coals.A new adsorption?desorption model derived based on thermodynamics is incorporated,particularly,the desorption hysteresis is considered.The reliability of the proposed adsorption-desorption isotherm is examined via validation tests.It is indicated that occurrence of desorption hysteresis is attributed to the adsorption-induced pore deformation.After injection ceases,the injected gas continues to propagate further from the injection well,while the pressure in the vicinity of the injection well experiences a significant drop.Although the adsorbed gas near the well also decreases,this decrease is less compared to that in pressure because of desorption hysteresis.The unceasing spread of CO_(2) and drops of pressure and adsorbed gas depend on the degree of desorption hysteresis and heterogeneity of coals,which should be considered when designing CO_(2) sequestration into coal seams.

Exploring the potential of olivine-containing copper-nickel slag for carbon dioxide mineralization in cementitious materials

Water-quenched copper-nickel metallurgical slag enriched with olivine minerals exhibits promising potential for the production of CO_(2)-mineralized cementitious materials.In this work,copper-nickel slag-based cementitious material(CNCM)was synthesized by using different chemical activation methods to enhance its hydration reactivity and CO_(2) mineralization capacity.Different water curing ages and carbonation conditions were explored related to their carbonation and mechanical properties development.Meanwhile,thermogravimetry differential scanning calorimetry and X-ray diffraction methods were applied to evaluate the CO_(2) adsorption amount and carbonation products of CNCM.Microstructure development of carbonated CNCM blocks was examined by backscattered electron imaging(BSE)with energy-dispersive X-ray spectrometry.Results showed that among the studied samples,the CNCM sample that was subjected to water curing for 3 d exhibited the highest CO_(2) sequestration amount of 8.51wt%at 80℃and 72 h while presenting the compressive strength of 39.07 MPa.This result indicated that 1 t of this CNCM can sequester 85.1 kg of CO_(2) and exhibit high compressive strength.Although the addition of citric acid did not improve strength development,it was beneficial to increase the CO_(2) diffusion and adsorption amount under the same carbonation conditions from BSE results.This work provides guidance for synthesizing CO_(2)-mineralized cementitious materials using large amounts of metallurgical slags containing olivine minerals.

Zonal activation of molecular carbon dioxide and hydrogen over dual sites Ni-Co-MgO catalyst for CO_(2) methanation:Synergistic catalysis of Ni and Co species

An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.

Electrochemical reduction of carbon dioxide to produce formic acid coupled with oxidative conversion of biomass

Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.

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.

Carbon dioxide capture, enhanced-oil recovery and storage technology and engineering practice in Jilin Oilfield, NE China

This paper systematically presents the established technologies and field applications with respect to research and engineering practice of CO_(2) capture,enhanced oil recovery(EOR),and storage technology in Jilin Oilfield,NE China,and depicts the available series of supporting technologies across the industry chain.Through simulation calculation+pilot test+field application,the adaptability of the technology for capturing CO_(2) with different concentrations in oilfields was confirmed.The low energy-consumption,activated N-methyl diethanolamine(MDEA)decarburization technology based on a new activator was developed,and the operation mode of CO_(2) gas-phase transportation through trunk pipeline network,supercritical injection at wellhead,and produced gas-liquid separated transportation was established.According to different gas source conditions,liquid,supercritical phase,high-pressure dense phase pressurization technologies and facilities were applied to form the downhole injection processes(e.g.gas-tight tubing and coiled tubing)and supporting anti-corrosion and anti-blocking techniques.In the practice of oil displacement,the oil recovery technologies(e.g.conical water-alternating-gas injection,CO_(2) foam flooding,and high gas-oil ratio CO_(2) flooding)and produced fluid processing technologies were developed.Through numerical simulation and field tests,three kinds of CO_(2) cyclic injection technologies(i.e.direct injection,injection after separation and purification,and hybrid injection)were formed,and a 10×10^(4) m^(3)/d cyclic injection station was constructed to achieve"zero emission"of associated gas.The CO_(2) storage safety monitoring technology of carbon flux,fluid composition and carbon isotopic composition was formed.The whole-process anti-corrosion technology with anticorrosive agents supplemented by anticorrosive materials was established.An integrated demonstration area of CO_(2) capture,flooding and storage with high efficiency and low energy-consumption has been built,with a cumulative oil increment of 32×10^(4) t and a CO_(2) storage volume of 250×10^(4) t.

Reduction of Aldehydes by Fe-H_2O-CO_2 System in Supercritical Carbon Dioxide

1 Introduction Nowadays, green chemistry has received increased attention. The use of water and scCO2 as a solvent or reagent is an important field for organic reactions and green chemistry both in laboratory and industry.

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.

Electrochemical Carbon Dioxide Reduction to Ethylene:From Mechanistic Understanding to Catalyst Surface Engineering

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)provides a promising way to convert CO_(2)to chemicals.The multicarbon(C_(2+))products,especially ethylene,are of great interest due to their versatile industrial applications.However,selectively reducing CO_(2)to ethylene is still challenging as the additional energy required for the C–C coupling step results in large overpotential and many competing products.Nonetheless,mechanistic understanding of the key steps and preferred reaction pathways/conditions,as well as rational design of novel catalysts for ethylene production have been regarded as promising approaches to achieving the highly efficient and selective CO_(2)RR.In this review,we first illustrate the key steps for CO_(2)RR to ethylene(e.g.,CO_(2)adsorption/activation,formation of~*CO intermediate,C–C coupling step),offering mechanistic understanding of CO_(2)RR conversion to ethylene.Then the alternative reaction pathways and conditions for the formation of ethylene and competitive products(C_1 and other C_(2+)products)are investigated,guiding the further design and development of preferred conditions for ethylene generation.Engineering strategies of Cu-based catalysts for CO_(2)RR-ethylene are further summarized,and the correlations of reaction mechanism/pathways,engineering strategies and selectivity are elaborated.Finally,major challenges and perspectives in the research area of CO_(2)RR are proposed for future development and practical applications.

煤矿充填固碳理论基础与技术构想

在国家“双碳”目标背景下,如何减少煤炭行业的碳排放、实现碳封存已成为亟待解决的难题。煤炭行业作为高碳化石能源生产者和主体碳排放源提供者,在生产和消费过程中引发的大宗固废堆存、大型采空区形成和大量CO_(2)排放是制约煤炭可持续开发利用与绿色健康发展的瓶颈所在。为协同解决二氧化碳封存与矿山固废消纳问题,将大宗固废处置、固废高值化利用、CO_(2)封存、采空区利用有机结合,提出了二氧化碳充填的理念,从碳汇能力评估角度界定了二氧化碳充填的3种类型。具体开展工作包括:①分析了CO_(2)充填料浆输运过程和矿化反应过程涉及到的基础理论,给出了各个过程的数学方程以及碳封存量计算公式,指出了温度、湿度等因素对矿化反应机理、碳封存量和充填体强度的影响规律。②总结了现阶段CO_(2)矿化的工艺方法、主要碱性工业固废的CO_(2)封存能力和CO_(2)矿化强化措施。在此基础上提出了基于直接湿法矿化和间接矿化的2种CO_(2)充填材料制备工艺,满足矿井充填的流动性、凝固特性和强度要求。③针对CO_(2)充填过程中的CO_(2)物理封存问题,提出了窄条带式胶结充填和综采架后胶结充填2种技术路径,前者通过在弱充填条带中构筑多贯通孔隙的充填体CO_(2)物理封存,后者借助充填支架和链式自行充填挡板在长壁工作面采空区中间断构筑充填带,控制顶板垮落,形成CO_(2)物理化学封存空间。④为了评估CO_(2)充填的碳平衡效果,依据全生命周期法界定了CO_(2)充填中碳足迹及碳消纳的计算边界。然后,梳理了CO_(2)充填过程中的碳足迹及碳消纳,分别考虑了CO_(2)的来源、用量、损耗、转化等因素。给出了包括原料运输、充填料浆制备、井下注入与充填等过程中的碳足迹及碳消纳计算方法。研究成果有望降低CO_(2)封存的能耗及成本,对煤炭绿色开采及其可持续开发利用具有深远的意义。

Accelerating net-zero carbon emissions by electrochemical reduction of carbon dioxide

Electroreduction of CO_(2)shows great potential for global CO_(2)utilization and uptake when collaborated with renewable electricity.Recent advances have been achieved in fundamental understanding and electrocatalyst development for CO_(2)electroreduction.We think this research area has progressed to the stage where significant efforts can focus on translating the obtained knowledge to the development of largescale electrolyzers,which have the potential to accelerate the transition of the current energy system into a sustainable and zero-carbon emission energy structure.In this perspective paper,we first critically evaluate the advancement of vapor-feed devices that use CO_(2)as reactants,from the point of view of industry applications.Then,by carefully comparing their performance to the state-of-the-art water electrolyzers which are well-established technology providing realistic performance targets,we looped back and discussed the remaining challenges including electrode catalysts,reaction conditions,mass transporting,membrane,device durability,operation mode,and so on.Finally,we provide perspectives on the challenges and suggest opportunities for generating fundamental knowledge and achieving technological progress toward the development of practical CO_(2)electrolyzers for the goal of building lowcarbon or/and net carbon-free economies.

新能源用钢管的应用现状、需求分析及思考

“双碳”战略下新能源及相关产业发展给钢管带来新的应用场景,对钢管的功能和性能提出新的需求。聚焦于碳捕获、利用与封存技术领域中的CO_(2)输送用管、氢能领域中的氢气输送用管和储能领域中的盐穴压缩空气储能用注采管,总结了新能源用钢管的应用现状和研究进展,分析了各领域用管需求,并就“双碳”背景下新能源用钢管的基础理论研究、关键技术开发和标准体系建设等方面进行了思考,提出了建议。

Carbon dioxide partial pressure and its diffusion flux in karst surface aquatic ecosystems:a review

Carbon dioxide(CO_(2))emissions from aquatic ecosystems are an important component of the karst carbon cycle process and also a key indicator for assessing the effect of karst carbon sinks.This paper reviewed the CO_(2)partial pressure(pCO_(2))and its diffusion flux(FCO_(2))in karst surface aquatic ecosystems,mainly rivers,lakes,and reservoirs,and their influencing factors summarized the methods for monitoring CO_(2)emissions in karst aquatic ecosystems and discussed their adaptation conditions in karst areas.The pCO_(2)and FCO_(2)decreased in the order of rivers>reservoirs>lakes,and the values in karst lakes were eventually significantly lower than those in global lakes.The pCO_(2)and FCO_(2)of karst aquatic ecosystems had patterns of variation with diurnal,seasonal,water depth and hydrological cycles,and spatial and temporal hetero-geneity.The sources of CO_(2)in karst waters are influenced by both internal and external sources,and the key spatial and temporal factors affecting the CO_(2)emissions from karst rivers,lakes,and reservoirs were determined in terms of physicochemical indicators,biological factors,and bio-genic elements;additionally,the process of human activity interference on CO_(2)emissions was discussed.Finally,a conceptual model illustrating the impacts of urban devel-opment,agriculture,mining,and dam construction on the CO_(2)emissions at the karst surface aquatic ecosystem is presented.Meanwhile,based on the disadvantages existing in current research,we proposed several important research fields related to CO_(2)emissions from karst surface aquatic ecosystems.

A Ruddlesden-Popper oxide as a carbon dioxide tolerant cathode for solid oxide fuel cells that operate at intermediate temperatures

Solid oxide fuel cells(SOFCs) that operate at intermediate temperatures of 600 to 800℃ have recently received increased attention due to their improved durability, more rapid startup and shutdown, better sealing and lower cost than their counterparts operate at high temperatures. Nevertheless, intermediatetemperature SOFCs(IT-SOFCs) with popular perovskite cathodes contain alkaline-earth elements, which are prone to reaction with carbon dioxide(CO_(2)), even when the CO_(2) content is comparatively low. In this work, an alkaline-earth metal-free Ruddlesden-Popper oxide, Nd_(1.8)La_(0.2)Ni_(0.74)Cu_(0.21)Ga_(0.05)O_(4+δ)(NLNCG), is developed for IT-SOFC cathodes. The cell is based on an electrolyte with 8%(mol) Y_(2)O_(3)-stabilized Zr O_(2)(8YSZ). The NLNCG cathode exhibits an excellent CO_(2) tolerance, as proven by thermogravimetry analysis,in situ X-ray diffraction, I-V-P test, and electrochemical impedance spectroscopy(EIS), and stability measurements. The anode-supported single-cell Ni O-YSZ|YSZ|NLNCG outputs a peak power density of 0.522 W·cm^(-2) at 800℃. These findings suggest that NLNCG could be a highly suitable cathode material with CO_(2) tolerance for IT-SOFCs.

Comprehensive modeling of frictional pressure drop during carbon dioxide two-phase flow inside channels using intelligent and conventional methods

Environmentally friendly nature of CO_(2),associated with its safety and high efficiency,has made it a widely used working fluid in heat exchangers.Since CO_(2)has strange thermophysical features,specific models are required to estimate its two-phase characteristics,particularly frictional pressure drop(FPD).Herein,a widespread dataset,comprising 1195 experimental samples for two-phase FPD of CO_(2)was adopted from 10 sources to fulfill this requirement.The literature correlations failed to provide satisfactory precisions and exhibited the average absolute relative errors(AAREs)between 29.29% and 67.69% from the analyzed data.By inspiring the theoretical method of Lockhart and Martinelli,three intelligent FPD models were presented,among which the Gaussian process regression approach surpassed the others with AARE and R^(2)values of 5.48% and 98.80%,respectively in the test stage.A novel simple correlation was also derived based on the least square fitting method,which yielded opportune predictions with AARE of 19.76% for all data.The truthfulness of the newly proposed models was assessed through a variety of statistical and visual analyses,and the results affirmed their high reliability over a broad range of conditions,channel sizes and flow patterns.Furthermore,the novel models performed favorably in describing the physical attitudes corresponding to two-phase FPD of CO_(2).Eventually,the importance of operating factors in controlling the FPD was discussed through a sensitivity analysis.