Catalytic Conversion Of CO2 Research Articles

Quantitative Insight into the Electric Field Effect on CO2 Electrocatalysis via Machine Learning Spectroscopy.

During chemical reactions, especially for electrocatalysis and electrosynthesis, the electric field is the most central driving force to regulate the reaction process. However, due to the difficulty of quantitatively measuring the electric field effects caused at the microscopic level, the regulation of electrocatalytic reactions by electric fields has not been well digitally understood yet. Herein, we took the infrared/Raman spectral signals of CO2 molecules as descriptors to quantitatively predict the effects of different electric fields on the catalytic properties. Taking the metal-doped graphitic C3N4 (g-C3N4) catalyst as an example, we theoretically investigated the adsorption mode and energy of CO2 molecules adsorbed on 27 distinct metal single-atom catalysts under different directions and intensities of electric field. Through a machine learning approach, a spectroscopy-property model between infrared/Raman spectral descriptors and adsorption energy/charge transfer was established, which quantified the facilitation of electric field effects on the CO2 catalytic conversion. Meanwhile, based on the attention mechanism, the catalytic insight of the relationship between spectra and adsorption modes was mined, and the inverse prediction of electric field strength from spectra was realized. This work opens a new quantitative pathway for monitoring and regulating electrocatalytic reactions using machine learning spectroscopy.

Research progress in catalytic conversion of CO2 and epoxides based on ionic liquids to cyclic carbonates

Research progress in catalytic conversion of CO2 and epoxides based on ionic liquids to cyclic carbonates

Overturning CO2 Hydrogenation Selectivity from CH4 to CO by Strong Ru-FeOx Interaction Arising from a Multilayer Epitaxial Structure.

The catalytic conversion of CO2 to CO through hydrogenation has emerged as a promising strategy for CO2 utilization, given that CO serves as a valuable C1 platform compound for synthesizing liquid fuels and chemicals. However, the predominant formation of CH4 via deep hydrogenation over Ru-based catalysts poses challenges in achieving selective CO production. High reaction temperatures often lead to catalyst deactivation and changes in selectivity due to dynamic metal evolution or agglomeration, even with a classic strong metal-support interaction. Herein, we have developed a FeOx/Ru/Rutile multilayer epitaxial structure by depositing a FeOx layer onto the epitaxially grown RuO2 nanolayers on the surface of rutile nanoparticles. This multilayer epitaxial structure transformed into a structure in which Ru nanoparticles were decorated with FeOx layers with ultrastable strong metal-support interaction (SMSI). Subsequently, the FeOx decoration on Ru nanoparticles effectively shifted the dominant product from CH4 to 95% CO during CO2 hydrogenation. Remarkably, this catalyst exhibits exceptional stability and can be operated stably at 550 °C for a long time without apparent deactivation. Compared with the dynamic changes observed in supported Ru nanoparticles, the interaction between Ru and FeOx maintains their electronic states at different reaction temperatures. Furthermore, this Ru-FeOx interaction inhibits H2 activation capability, CO adsorption, and subsequent hydrogenation of CO. The transformation strategy employed here, which utilizes initial multilayer epitaxial structures, can be applied to construct SMSI to enhance metal catalysts' catalytic performance.

Active Sites for CO2 Hydrogenation to Methanol: Mechanistic Insights and Reaction Control.

Catalytic CO2 conversion to methanol is a promising way to extenuate the adverse effects of CO2 emission, global warming and energy shortage. Understanding the fundamental features of CO2 activation and hydrogenation at the molecular level is essential for carbon utilization and sustainable chemical production in the current climate crisis. This review explores the recent advances in understanding the design of catalysts with desired active sites, including single-atom, dual-atom, interface, defects/vacancies and promoters/dopants. We focused on the design of various catalytic systems to enhance their catalytic performances by stabilizing active metal in a catalyst, identifying the unique structure of active species, and engineering coordination environments of active sites. Mechanistic insights provided by advanced operando and in situ spectroscopies were also discussed. Moreover, the review highlights the key factors affecting active sites and reaction mechanisms, such as local environments, oxidation states, and metal-support interactions. By integrating recent advancements and relating knowledge gaps, this review aims to endow an inclusive overview of the field and guide future research toward more efficient and selective catalysts for CO2 hydrogenation to methanol.

Advances in Carbon Dioxide Catalytic Conversion and Applications

To achieve the global climate goals set out in the Paris Agreement, reducing carbon dioxide (CO2) emissions and utilizing resources have become key areas of focus within international energy technology research and development. CO2 can be converted into high-value chemicals, including hydrocarbons, alcohols and hydrocarbons, through the catalytic technology. This process can potentially address environmental issues while generating economic benefits. This paper presents a review of the principal products resulting from the catalytic conversion of CO2, together with an examination of their practical applications. These include hydrogenation of olefins, light aromatics, methanol, polyols, and synthetic bioconversion technologies. The development of catalysts with high conversion and selectivity represents a key area of current research. In the future, it will be necessary to combine physical, chemical, and biological technologies to establish an engineered heterogeneous carbon sequestration technology system to achieve the efficient conversion and utilization of CO2.

Efficient paddle-wheel copper cluster-based metal-organic framework for catalytic conversion of CO2 to oxazolidinones under mild conditions

Efficient utilization of CO2 and its conversion into high-value-added products contribute to mitigating environmental issues such as the greenhouse effect. Among these methods, the carboxylation cyclization of CO2 with propargylic amine represents a green and atom-economical approach. Developing cost-effective catalyst that can promote this reaction under mild condition is desirable but challenging. Herein, a unique two-dimensional (2D) metal–organic framework (MOF) {[Cu(QCA)2]∙0.5DMF∙0.5H2O}n (1) (QCA =6-quinolinecarboxylic acid, DMF = N,N-dimethylformamide) have been synthesized and thoroughly characterized. Compound 1 was constructed from paddle-wheel dinuclear copper clusters [Cu2(COO)4] and carboxylate ligands, presenting a two-dimensional framework with new topology. Stability tests indicate that compound 1 undergoes reversible structural changes in different solvents and exhibits good thermal stability. 1 as heterogeneous catalyst enabled the transformation of CO2 and propargylic amine into oxazolidinones under mild conditions with broad substrate generality. In addition, 1 could maintain its catalytic performance with five continuous reactions. This work presents an infrequent example of a 2D noble metal free MOF-based catalyst that shows high catalytic efficiency under mild conditions.

Conversion of CO2 into Synthetic Motor Fuels

The process of CO2 conversion into synthetic hydrocarbons including the stages of synthesis gas production on the catalyst NIAP 06-06 and hydrocarbon synthesis by the Fischer-Tropsch method on a bifunctional zeolite-containing catalyst has been investigated. Experimental studies of the process of catalytic conversion of CO2 into synthesis gas were carried out in order to obtain gas with the ratio of H2/CO close to the required ratio for Fischer-Tropsch synthesis. The possibility of obtaining gasoline and diesel fractions of hydrocarbons with a high content of isomeric structures that increase the performance characteristics of motor fuels has been shown. The yield of hydrocarbons C5+ with 1 m3 of initial CO2 and H2 at the synthesis temperature of 220 °C is found to be 44.5 g.

Single-Pass Demonstration of Integrated Capture and Catalytic Conversion of CO2 from Simulated Flue Gas to Methanol in a Water-Lean Carbon Capture Solvent.

Here, we demonstrate an integrated semibatch simultaneous CO2 capture and conversion to methanol process using a water-lean solvent, N-(2-ethoxyethyl)-3-morpholinopropan-1-amine (2-EEMPA), that serves as both the capture solvent and subsequent condensed-phase medium for the catalytic hydrogenation of CO2. CO2 is captured from simulated coal-derived flue gas at a target >90 mol % capture efficiency, with a continuous slipstream of CO2-rich solvent delivered to a fixed bed catalytic reactor for catalytic hydrogenation. A single-pass conversion rate >60 C-mol % and selectivity >80 C-mol % are observed for methanol at relatively low temperatures (<200 °C) in the condensed phase of the carbon capture solvent. Hydrogenation products also include higher alcohols (e.g., ethanol and propanol) and hydrocarbons (e.g., methane and ethane), suggesting that multiple products could be made offering adaptability with varied CO2-derived products. Catalyst activity and selectivity are directly impacted by the water content in the capture solvent. Anhydrous operation provides high catalyst activity and productivity, suggesting that water management will be a critical parameter in real-world operation. Ultimately, we conclude that the integrated capture and catalytic hydrogenation of CO2 are chemically viable and potentially more energetically efficient and cost-effective than conventional separate capture and conversion approaches.

Oxygen vacancies–elusive but common catalytic key defects for thermal upgrading of CO2 to CH4, CO and CH3OH

Single carbon products (C1 compounds) are simple but important chemicals in the road towards energy transition. Catalytic conversion of CO2 with H2 (desirably renewable) can be performed over reducible oxides supporting transition metals to obtain products such as CH4, CO and MeOH. Oxygen vacancies (O-vacancies), which are inherent defects of reducible metal oxides, play an enormous role in driving the catalytic performance (activity, selectivity, stability) for the desired reactions. Yet, the assessment of O-defects at realistic conditions is often complex. Only few techniques can provide direct evidence for their existence and influence in CO2 activation. Among them, electron paramagnetic spectroscopy (EPR), Raman spectroscopy, scanning probe microscopies (SPM) and environmental transmission electron microscopy (ETEM) are nowadays the most informative. In most cases, however, the measurements require reaction conditions far away from CO2 valorization applications. Although great efforts have been fruitful in explaining and demonstrating the huge importance of O-vacancies in CO2 catalysis, still ambiguous or erroneous interpretations about structure-function correlations involving O-vacancies are found in literature, especially, when information is not properly gathered, e.g., by O 1s ex-situ X-ray photon spectroscopy (XPS). Moreover, despite the recognized importance of O-vacancies for CO2 valorization, critical literature compilations about their effects in thermal processes are scarce. Herein, we attempt to contribute in closing this gap by integrally encompassing representative investigations on the thermo-catalytic production of CH4, CO and MeOH. Particularly, we emphasize in the proper selection of assessment tools (direct/indirect) to unambiguously establish structure-function relationships to design optimized O-defective catalysts for the targeted compounds.

ZIF-8 Porous Liquids with Different Sterically Hindered Solvents and Porous Guests for Catalytic Conversion of Carbon Dioxide.

Utilizing carbon dioxide (CO2) as a raw material is an effective way to reduce carbon emissions, and developing catalytic systems with high catalytic activity and stability is crucial for the efficient utilization of CO2. Porous liquids (PLs) with both permanent pores and fluidity have great potential in the fields of catalysis, gas sorption, and storage. Nevertheless, the catalytic performance of PLs is affected by many factors; therefore, further study is needed. Herein, we proposed a general strategy to construct a series of type III PLs with different chemical structures of sterically hindered solvents and different microstructures of porous guests. Benefiting from the unique microstructures, the as-prepared PLs exhibit great potential in catalyzing the reaction of CO2 with propylene oxide under suitable conditions. Moreover, their catalytic activity exceeds that of pure sterically hindered solvents without a porous guest loading. The influences of the nucleophilicity of the anion of the sterically hindered solvent and the microstructure of the porous guests on the catalytic activity and the catalytic stability of the PLs were analyzed. Meanwhile, the mechanism of the catalytic conversion of CO2 was proposed, which is of great significance for the design and development of the subsequent PL catalysts.

Investigation of highly efficient CO2 hydrogenation at ambient conditions using dielectric barrier discharge plasma

The increasing utilization of CO2 for synthesizing high-value fuels or essential chemicals is a potentially effective approach to mitigating global warming and climate change. Compared to thermal catalytic CO2 conversion under hash operating conditions (400–500°C, 10 ​MPa), non-thermal plasma can overcome kinetic barriers and trigger reactions beyond thermal equilibrium at ambient temperature and pressure. In this study, the effects of operating conditions (discharge frequency, input power, and gas flow rate) and geometrical parameters (discharge length, discharge gap, and dielectric materials) have been extensively analyzed using typical cylindrical dielectric barrier discharge (DBD) plasma. The discharge characteristics changed by operating conditions (including waveforms of applied voltage and current) are compared, indicating higher applied voltage and lower gas flow rate can strengthen the filamentary discharges. The results demonstrate CO2 conversion rate increases with the increase of applied voltage and the decrease of CO2/H2 ratio, achieving its maximum value of 43.0% at 20 ​mL/min. The highest energy efficiency of 3771.9 ​μg/kJ for CO generation is obtained at the applied voltage of 5.5 ​kV and gas flow rate of 40 ​mL/min, respectively. Besides, the constructure of plasma reactor also impacts the performance of CO2 conversion. On the one hand, the discharge gap has a significant role in the variation of CO2 conversion and product selectivity, which is attributed to the electric field density and corresponding electron-induced reaction. On the other hand, the circulating water-cooling jacket was used to find out the influence of reaction temperature, which switched the product from CO to CH4. This work will pave the way for a sustainable alternative towards future CO2 conversion and utilization.

Organic and Non‐Precious Metal Photosensitizers for Photocatalytic CO2 Reduction

AbstractCarbon dioxide (CO2) is the primary greenhouse gas responsible for global warming, posing a significant challenge to the global environment. To reduce CO2 emission and support the sustainable development, efficient conversion of CO2 into chemical feedstocks has gained a lot of attention. One promising strategy inspired by natural photosynthesis is solar‐driven CO2 reduction, which uses appropriate photocatalytic systems to generate CO, HCOOH, CH4, CH3OH, etc. However, developing low‐cost, environmentally friendly, and non‐toxic materials for the catalytic conversion of CO2 remains a significant challenge. Light‐absorbing photosensitizers play an important role in photocatalytic systems. Recently, non‐precious metal photosensitizers such as organic compounds and earth‐abundant metal complexes have been intensively studied for developing low‐cost photocatalytic systems. This review focuses on recent reports on organic and non‐precious metal photosensitizers for photocatalytic CO2 reduction.

Capture and catalytic conversion of CO2 from marine and offshore applications – A review

Abstract This contribution examines recent advances in modeling fluid dynamics and capture/conversion of CO2 from marine and offshore applications in packed-bed columns/trickle-bed reactors subjected to static inclination, externally-induced rolling and heaving motions. Breaking the axial symmetry of the two-phase flow once the packed bed system is tilted results in a significant decrease in process performance, the extent of which is determined by the magnitude of the tilt and the column/reactor diameter. Only the conversion of CO2 from marine engine emissions on-board large cargo ships via catalytic cycloaddition of CO2 to styrene oxide in multiphase large-diameter trickle-bed reactors increases slightly with increasing reactor inclination. Under the externally induced column/reactor oscillations, CO2 capture/conversion performance shifts toward the steady-state solution of the vertical column/reactor as the asymmetry between the two inclined positions decreases. Oscillating (between two inclined symmetrical positions) and heaving packed-bed columns/trickle-bed reactors generate an oscillating performance around the steady-state solution of the vertical static position, which is driven by the amplitude and period of the angular and heaving motions via the continuous evolution of the intensity of the reverse secondary flow and by the magnitude of the reactor/column diameter. The catalytic conversion of CO2 captured from marine emissions via an integrated process coupling reverse water-gas shift reaction and methanol synthesis in a fixed-bed reactors network system shows a remarkable enhancement with the addition of H2O adsorbent to the reaction systems in the sorption-enhanced process periods.

Emerging 2D MXene quantum dots for catalytic conversion of CO2

MXene is an emerging material for converting carbon dioxide (CO2) into valuable products because of its robust physical and chemical properties. The high specific surface area (SSA), conductivity, and stability of the MXene make it an attractive material for the catalytic conversion of CO2. The pristine MXene possessed poor catalytic properties as compared to their composites. This study briefly discussed the magical properties and advanced synthesizing routes of MXene and MXene quantum dots (MQDs). In addition, the oxidation of the MXene is responsible for altering its chemical composition, and the factors used to oxidize the MXene were discussed in detail. Furthermore, the mechanism of hydrogenation, chemical, electrocatalytic, and photocatalytic reduction of CO2 has been discussed. Finally, the MXene quantum dots (MQDs) for photocatalytic conversion of CO2 for the first time also present the future challenges and prospectus associated with MXene.

Ionic Liquid‐Functionalized Porous Materials for Catalyzing CO2 Cycloaddition Reaction

AbstractIonic liquids (ILs) are incorporated into traditional porous materials to create ILs‐functionalized porous materials, which exhibit excellent absorption capacity and good catalytic activity for CO2. As a result, they are extensively utilized in the chemical conversion of CO2. This paper specifically focuses on the utilization of ILs‐functionalized organic porous materials, ILs‐functionalized inorganic porous materials, and ILs‐functionalized organic‐inorganic hybrid porous materials in the conversion of CO2. The synergistic effects of combining ILs with porous materials in CO2 conversion are thoroughly discussed. Furthermore, an in‐depth analysis is provided regarding the potential prospects and future applications of utilizing ILs‐functionalized porous materials within the broader realm of catalytic CO2 conversion technologies.

A Mini-Review on Recent Developments and Improvements in CO2 Catalytic Conversion to Methanol: Prospects for the Cement Plant Industry

A Mini-Review on Recent Developments and Improvements in CO2 Catalytic Conversion to Methanol: Prospects for the Cement Plant Industry

Role of Ca in Ni-Ca/Fumed-SiO2 Catalysts for CO2 Catalytic Conversion to Methane

AbstractThis study investigates the role of calcium in facilitating the carbon dioxide methanation reaction over nickel supported on fumed-SiO2 catalysts. The wet impregnation method was used to prepare Ni/fumed-SiO2 catalysts with three different Ca loadings for CO2 conversion. As part of the investigation into the effects of Ca concentration and reaction conditions on the structural and morphological properties of the catalysts, various techniques including XRD, BET, SEM, TPR and TEM were used for both fresh and used catalyst samples. The findings showed that the addition of 0.5% Ca increases the catalyst reducibility, promotes dispersion of Ni sites on the surface of fumed SiO2 support and prevents the metal from agglomerating. Evaluation of catalytic results showed that the performance of 10%Ni-0.5Ca/fumed-SiO2 was superior to the other tested catalysts, with CO2 conversion and CH4 yield of 76% and ~ 40% at 650 °C, respectively.

Synthesis of UiO-66-NH2@PILs core-shell composites for CO2 conversion into cyclic carbonates via synergistic catalysis under solvent- and additive-free conditions

Metal-organic frameworks (MOFs) have been hybridized with other functional materials, such as ionic liquids, covalent organic frameworks (COFs), and metallic nanoclusters, to fabricate composite materials. These composites possess the structural characteristics of their individual components and exhibit synergistic properties. In this work, we demonstrate the synthesis of core-shell structure UiO-66-NH2@PILs-x composite materials by encapsulating MOFs within ionic polymers (PILs) with varying thicknesses of PILs shell. These hybrid materials serve as bifunctional catalysts for the conversion of CO2 into cyclic carbonates under solvent- and additive-free conditions through a synergistic catalytic effect facilitating the conversion of CO2 into cyclic carbonates under solvent- and additive-free conditions through synergistic catalytic effect, exhibiting superior catalytic performance and excellent recyclability. This MOFs-based composite material provides a competitive approach for CO2 catalytic conversion.

Reaction-induced unsaturated Mo oxycarbides afford highly active CO2 conversion catalysts.

Sustainable CO2 conversion is crucial in curbing excess emissions. Molybdenum carbide catalysts have demonstrated excellent performances for catalytic CO2 conversion, but harsh carburization syntheses and poor stabilities make studies challenging. Here an unsaturated Mo oxide (Mo17O47) shows a high activity for the reverse water-gas shift reaction, without carburization pretreatments, and remains stable for 2,000 h at 600 °C. Flame spray pyrolysis synthesis and Ir promoter facilitate the formation of Mo17O47 and its in situ carburization during reaction. The reaction-induced cubic α-MoC with unsaturated Mo oxycarbide (MoOxCy) on the surface serves as the active sites that are crucial for catalysis. Mechanistic studies indicate that the C atom in CO2 inserts itself in the vacancy between two Mo atoms, and releases CO by taking another C atom from the oxycarbide to regenerate the vacancy, following a carbon cycle pathway. The design of Mo catalysts with unsaturated oxycarbide active sites affords new territory for high-temperature applications and provides alternative pathways for CO2 conversion.

Synthesis of metal-phenanthroline-modified hypercrosslinked polymer for enhanced CO2 capture and conversion via chemical and photocatalytic methods under ambient conditions

Catalytic conversion of CO2 into valuable chemicals is a promising approach to mitigate the greenhouse effect and alleviate energy shortages. Hypercrosslinked polymers (HCPs) offer a scalable and stable platform for this conversion, but they often suffer from low CO2 adsorption and activation capabilities, necessitating high temperatures and pressures for effectiveness. To overcome these limitations, nitrogen-based CO2-philic active sites have been integrated into the structure of HCPs, enhancing CO2 attraction and leading to superior adsorption performance. The incorporation of cobalt ions further bolsters CO2 affinity, with HCP-PNTL-Co-B achieving the highest observed adsorption heat of 33.0 kJ·mol-1 alongside a substantial 2.0 mmol·g-1 CO2 uptake. These modified HCPs exhibit higher yields and reaction rates in cycloaddition reactions with cocatalyst tetrabutylammonium bromide at room temperature and atmospheric pressure, while HCP-1,10-phenanthroline (PNTL)-Co-B demonstrates a higher CO production rate (2,173 μmol·g-1·h-1) and selectivity (84%) in photocatalytic reduction reaction. This research has successfully achieved outstanding carbon dioxide capture and conversion performance at room temperature and atmospheric pressure by introducing CO2-philic active sites and cobalt ions into HCPs via facile one-step polymerization. This study provides a new method to design highly efficient organic catalysts for CO2 conversion.