CO2 Utilization Research Articles

Pt‐Mo₂N Catalyst Formed by Inverse Sintering for the Reverse Water‐Gas Shift Reaction

AbstractThe reverse water‐gas shift (RWGS) reaction is significant for the resource utilization of CO2. However, this reaction requires high temperatures and metal catalysts are prone to agglomeration, leading to loss of activity. In this work, a Pt catalyst supported on Mo₂N formed via phase transition and metal reverse sintering under a high‐temperature NH₃ atmosphere is developed. This catalyst exhibits excellent RWGS activity, achieving a CO production rate of 294.8 mmolgcat−1 h−1 at 623 K, with CO selectivity maintained at 93%. Moreover, under continuous testing conditions for 100 h, the catalyst's activity shows no significant decline. Notably, further investigation reveals that the surface reaction mechanism at 623 K differs from the previously reported associative mechanism, instead following a redox mechanism in the presence of H₂. This research not only provides a deeper theoretical understanding of the mechanism of CO2 hydrogenation but also offers valuable insights for developing novel and efficient metal catalyst regeneration technologies.

CO2 Utilization and Sequestration in Organic and Inorganic Nanopores During Depressurization and Huff-n-Puff Process

CO2 Utilization and Sequestration in Organic and Inorganic Nanopores During Depressurization and Huff-n-Puff Process

Sensitivity analysis of a dual-continuum model system for integrated CO2 sequestration and geothermal extraction in a fractured reservoir

Depleted hydrocarbon reservoirs are considered as the most feasible option for CO2 geological sequestration and utilization. Most of the hydrocarbon reservoirs are naturally fractured. Simulation of fluid flow and heat transfer in these fractured formations remains a significant challenge in reservoir engineering. In this study, a dual-continuum model is developed to simulate integrated CO2 sequestration and CO2-circulated geothermal extraction in a fractured reservoir block in North Oman. The high-dimensional sensitivity of key parameters controlling CO2-brine flow and heat transfer in this matrix-fracture system is quantitatively evaluated by an efficient surrogate modeling approach. The surrogate models are constructed and validated based on a suite of physics-based model simulations. It is found that fracture permeability dominates the CO2 injectivity, storage, circulation and associated geothermal extraction. Response surface analysis shows that the flow area density between matrix-fracture and matrix block length controls the flux interaction between matrix and fracture formations. In contrast, the fracture aperture shows negligible influence in the dual-continuum modeling system. Particularly, sensitivity varying with locations on the response surface is analyzed for defined performance indicators.

Investigating proton shuttling and electrochemical mechanisms of amines in integrated CO2 capture and utilization

Carbon capture and utilization (CCU) technologies present a promising solution for converting CO2 emissions into valuable products. Here we show how amines, such as monoethanolamine (MEA) and 2-amino-2-methyl-1-propanol (AMP), influence the electrochemical CO2 reduction process in an integrated CCU system. Using in situ spectroscopic techniques, we identify the key roles of carbamate bond strength, proton shuttling, and amine structure in dictating reaction pathways on copper (Cu) and lead (Pb) electrodes. Our findings demonstrate that on Cu electrodes, surface blockage by ammonium species impedes CO₂ reduction, whereas on Pb electrodes, proton shuttling enhances the production of hydrocarbon products. This study provides additional insights into optimizing CCU systems by tailoring the choice of amines and electrode materials, advancing the selective conversion of CO₂ into valuable chemicals.

Preparation of nano Cu-Mo2C interface supported on ordered mesoporous biochar of ultrahigh surface area for reverse water gas shift reaction

High conversion rate and selectivity are challenges for CO2 utilization through catalytic reverse water gas shift (RWGS) reaction. Herein, a novel mesoporous biochar (MB) supported Cu-Mo2C nano-interface was prepared by consecutive physical activation of coconut shells followed by carbothermal hydrogen reduction of bimetal. As compared with traditional carbon materials, this MB exhibited ultra-high specific surface area (2693 m2 g–1) and mesopore volume of mesopore (0.81 cm3 g–1) with a narrow distribution (2–5 nm), responsible for the high dispersion of binary Cu-Mo2C sites, CO2 adsorption and mass transfer in the reaction system. Moderate carbothermal reduction led to the sufficient reduction of Mo ion with carbon matrix of MB and dispersive growth of nano Cu-Mo2C binary sites (~ 6.1 nm) on the surface of MB. Cu+ species were formed from Cu0 via electron transfer and showed high dispersion with simultaneous boosted bimetal loading due to the strong interaction between nano Mo2C and Cu. These were advantageous to the intrinsic activity and stability of the Cu-Mo2C binary sites and their accessibility to the reactant molecules. Under the RWGS reaction conditions of 500 °C, atmospheric pressure, and 300,000 ml/g/h gas hour space velocity, the CO2 conversion rate over Cu-Mo2C/MB reached 27.74 × 10–5 molCO2/gcat/s at very low H2 partial pressure, which was more than twice that over traditional carbon supported Cu-Mo2C catalysts. In addition, this catalyst exhibited 99.08% CO selectivity and high stability for more than 50 h without a decrease in activity and selectivity. This study offers a new development strategy and a promising candidate for industrial RWGS.Graphical

Homogeneous Catalysis in N-Formylation/N-Methylation Utilizing Carbon Dioxide as the C1 Source.

The growing emphasis on sustainable chemistry has driven research into utilizing carbon dioxide (CO2) as a nontoxic, abundant, and cost-effective C1 building block. CO2 offers a promising avenue for direct conversion into valuable chemicals ranging from fuels to pharmaceuticals. This review focuses on the utilization of CO2 for reductive N-formylation/N-methylation reactions of various amines, providing advantages over conventional methods involving toxic CO and other methylating reagents. The approach employs readily available reductants such as silane, borane reagents, and hydrogen (H2). The discussion encompasses recent developments in transition metal and organocatalyst systems for these reactions, highlighting mechanistic interpretations and factors influencing product selectivity.

A MOF@MOF S-scheme Heterojunction with Lewis Acid-Base Sites Synergistically Boosts Cocatalyst-Free CO2 Cycloaddition.

The photocatalytic cycloaddition reaction between CO2 and epoxide is one of the most promising green routes for CO2 utilization, for which high performance photocatalysts are intensely desired. Herein, we have constructed an S-scheme heterojunction of MIL-125@ZIF-67 modified by amino groups, which achieves a cyclic carbonate yield of as high as 99 % without employing any co-catalyst, outperforming the previously reported photocatalysts. In-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and in-situ electron paramagnetic resonance (EPR) spectroscopy reveal the important role of photogenerated electron migration from Lewis acid (Co) sites to the O atom of epoxide in triggering its ring-opening (the rate-determining step of CO2 cycloaddition reaction) under the assistance of photogenerated hole. Synergistically and concurrently, the Lewis base (amino groups) sites activate CO2 to CO2*, facilitating the following CO2 cycloaddition. Such a synergistic effect provides a most favorable approach to design efficient heterogeneous photocatalysts with dual/multiple-active sites for CO2 cycloaddition reaction.

Theoretical predictions of CO2, H2 and H2O adsorption mechanisms on M2C-MXene: Selectivity and potential application insights

M2C-MXenes, owing to their abundant adsorption sites, exhibit significant potential in CO2 capture, utilization, and storage (CCUS) and hydrogen energy applications, contributing to hydrogen utilization and global carbon reduction, and thus solving intractable energy and environmental problems. However, the extensive variety of M2C compounds poses challenges to the systematic evaluation of their applications in these fields. The exploration of the adsorption properties of M2Cs is a key fundamental aspect of these studies, and therefore, this study employs calculations across 456 adsorption systems to elucidate the adsorption mechanisms of 19 M2C compounds for small molecules (CO2, H2 and H2O). The results indicate that these M2C materials possess structural stability and metallic characteristics, with periodic variations in the d-band center aligning with trends in CO2 adsorption energy. Notably, molecular orientation impacts adsorption energy more significantly than adsorption sites, particularly for CO2, while M2C compounds primarily exhibit physical adsorption towards H2. Specifically, Sc2C preferentially adsorbs CO2 in atmospheric conditions, and shows chemical adsorption towards H2O, but exhibits negligible adsorption for H2; conversely, Cr2C demonstrates higher adsorption potential for H2. Both materials exhibit favorable thermodynamic stability, suggesting Sc2C is suitable for CCUS applications, while Cr2C holds promising prospects for hydrogen storage.

Mechanochemical Synthesis of High-Entropy MOF-74 with Multiple Active Sites for CO2 Adsorption and Synergistic Conversion.

Compared with monometallic metal-organic frameworks (MOFs), the synergistic effect of multiple metals significantly enhances the catalytic performance of the CO2 cycloesterification reaction, leading to improved CO2 adsorption and catalytic conversion capabilities. To investigate this concept, a high-entropy MOF-74 (HE-MOF-74) with a uniform distribution of five distinct metal ions (Zn2+, Mg2+, Ni2+, Co2+, and Cu2+) was successfully synthesized using a straightforward mechanical ball milling technique and comprehensively characterized (including structural, morphological, and physicochemical properties). The results reveal that HE-MOF-74 exhibits significantly increased specific surface area and CO2 adsorption capacity compared with those of monometallic MOF-74. The presence of multiple unsaturated metal centers as Lewis acid sites, oxygen atoms linking the metals, and ligand-based hydroxyl groups serving as base sites enable efficient immobilization of CO2 into cyclic carbonate. This study introduces a novel synthetic approach for the green and efficient production of HE-MOF-74 and proposes a new application for CO2 utilization.

Enhanced Selectivity to Methanol in CO2 Hydrogenation on CuO/ZrO2 Catalysts by Alkali Metal Modification

AbstractIn order to alleviate the influence of greenhouse effect on global climate change, the effective utilization of CO2 to prepare fine chemicals should be paid more attention to, however, which is greatly blocked by the catalyst with low efficiency. Here, alkali metal (Li, Na, or K) are employed as a modification aid to prepare CuO/ZrO2 catalyst for CO2 hydrogenation to methanol. The effects of alkali metal on physicochemical properties and catalytic activities of CuO/ZrO2 catalyst were studied in detail by the XRD, N2‐physisorption, ICP‐OES, SEM/EDS, H2/N2O/CO2/NH3‐chemisorption, and evaluation test. The results verified that the use of complex combustion method enabled the uniform combination of all components in precursor. High‐temperature calcination (700 °C) further enhanced the strong interaction and synergistic effect between Cu and ZrO2. Most importantly, the introduction of alkali metal effectively altered the structure and catalytic activity of CuO/ZrO2 catalysts. However, the selectivity to methanol increased while the CO2 conversion decreased regardless of different kinds of alkali metal being introduced to the CuO/ZrO2 catalysts. For example, CuO/ZrO2 catalyst modified by K exhibited excellent performance for methanol production that 98.9% selectivity of methanol based on 8.8% conversion of CO2 after 48 h online reaction.

Biological CO2 Utilization; Current Status, Challenges, and Future Directions for Photosynthetic and Non-photosynthetic Route

Biological CO2 Utilization; Current Status, Challenges, and Future Directions for Photosynthetic and Non-photosynthetic Route

Optimization of cost-effectiveness and environmental impact in advanced membrane technologies for CO2 capture and utilization

Optimization of cost-effectiveness and environmental impact in advanced membrane technologies for CO2 capture and utilization

Non-Noble Metal Anchored 2D Covalent Organic Framework for Ambient CO2 Fixation to High-Value Compounds.

The catalytic functionalization of CO2 into high-value compounds comprises a promising approach to mitigate its atmospheric content and sustainable generation of fine chemicals. Herein, we report application of a crystalline, nano-porous 2D COF (ET-BP-COF) for utilization of CO2. The ET-BP-COF features a unique 2D kagome (kgm) topology composed of hexagonal and triangular 1D channels decorated with bipyridine sites, which were exploited for covalent anchoring of eco-friendly Cu(I) by post-synthetic method. The Cu(I) engrafted COF was applied as a recyclable catalyst for coupling CO2 with alkynes to generate two high-value compounds, α-alkylidene cyclic carbonates (α-ACCs) and 2-oxazolidinones. Notably, Cu(I)@ET-BP-COF demonstrated excellent catalytic performance for transforming propargylic amine and CO2 to 2-oxazolidinone, an essential building block for antibiotics. Besides, an efficient transformation of propargylic alcohols to generate α-ACCs, valuable commodity chemicals, has been achieved by utilizing carbon dioxide. Further, detailed theoretical simulations disclosed the insight mechanistic path of Cu(I) catalyzed coupling of CO2 with alkynes to produce 2-oxazolidinones and α-ACCs. Significantly, Cu(I)@COF was reusable for multiple cycles without losing framework rigidity and catalytic performance. This study showcases the potential application of ET-BP-COF for stable anchoring of eco-friendly metals as catalytic sites for effective utilization of CO2 to produce two high-value products.

Substoichiometric La0.8MnO3-based nanocomposites for PGM-free activation of CH4: Ni or Cu? Surface or bulk?

Methane is a renewable fuel when derived from biogas upgrading or by CO2 capture and utilization, with the possibility of fully replacing natural gas in the already established gas infrastructure and engines. However, being a potent greenhouse gas, its use as fuel demands a sustainable activation procedure, to convert any residual traces of unburned CH4 into CO2, a challenging reaction especially at near-stoichiometric conditions typical of Three-Way Catalytic systems (TWC). To avoid expensive noble metals, we developed cheaper alternative catalysts: A-site deficient LaMnO3-based nanocomposites incorporating Ni and Cu. These elements were introduced either as B-site dopants in the perovskite lattice or deposited via Ammonia-driven Deposition-Precipitation (ADP) on the perovskite surface, in both cases yielding metal nanoparticles (NPs) after a reductive treatment. Characterization encompassed various techniques: XRD, N2 physisorption, SEM-EDX, XPS, H2-TPR, HAADF STEM-EDX. CH4 oxidation to CO2 under stoichiometric O2 served as the probe reaction, as model for TWC conditions in methane-fed engines. The LaMn-perovskite itself displayed a promising activity thanks to favourable morphological and redox features (50 % and 90 % CH4 conversion at 581 °C and 678 °C, respectively); further improvements could be obtained upon Ni and Cu loading. The best performances were achieved by: i) the catalyst prepared by Ni-ADP (50 % and 90 % CH4 conversion at 517 °C and 635 °C), featuring high Ni surface concentration and NPs density and a synergy with the perovskite support, as opposed to the low Ni surface concentration on B-site doped samples; ii) the reduced Cu-doped catalyst (50 % and 90 % CH4 conversion at 508 °C and 645 °C), thanks to the high activity of reduced Cu species, the low NPs size and good metal-support interaction, in contrast to the strong NPs agglomeration of the Cu-ADP catalyst. Among the two most active catalysts, a better long-term stability was retained by the Cu-doped sample. This work laid the foundation for the development of alternative CH4 oxidation catalysts at the stoichiometric air-to-fuel ratio, cheaper than commercial Pd-based ones.

Enhanced microwave-catalytic performance for CO2 oxidative propane dehydrogenation by acidified and Bi-doped ZnO-based microwave catalysts

The oxidative dehydrogenation of propane by carbon dioxide (CO2-ODHP) has great potential in producing propylene. Resource utilization of CO2 will be the dominant trend in the future to mitigate environmental problems and cope with the growth in energy demand. However, simultaneously achieving high propane conversion, high propylene selectivity, and high CO2 conversion at low temperatures remains challenging. Herein, we report a novel efficient microwave catalyst (1.0-Zn4Bi1/Silicalite-1+SiC) by doping Bi on ZnO/Silicalite-1 and then acid treatment. The (1.0)-Zn4Bi1/Silicalite-1+SiC microwave catalyst exhibited 92 % C3H8 conversion, 84 % C3H6 selectivity, and 45 % CO2 conversion under microwave mode, significantly better than under the thermocatalysis (without microwave: 27 % C3H8 conversion, 92 % C3H6 selectivity, and 14 % CO2 conversion). The CO2 capture capacity was improved by adding Bi to ZnO/Silicalite-1. In addition, acid modification increased the propane and CO2 conversion by 1.9 and 1.3 times, respectively. Notably, acid treatment enriched the pore structure of the catalysts, altered surface acidity and alkalinity, and promoted C3H8 and CO2 activation and C3H6 desorption. In particular, the acid treatment enriches the state of the presence of Zn species in the catalyst. Microwave irradiation reduces the apparent activation energy of the catalytic system and accelerates the removal of coke from the catalyst surface. Microwave catalysis can activate CO2 and propane at lower temperatures than thermocatalysis.

Hydrazino-containing Zr-MOF for enhanced Lewis acid-base catalysis of CO2 fixation into cyclocarbonate

Developing an effective catalyst for converting CO2 into high-value chemicals is greatly desirable but remains a big hurdle. Herein, Zr-MOF derivative-bearing hydrazino groups were synthesized by mixing the ligands of terephthalic acid and 4-hydrazinobenzoic acid (HBA), resulting in UiO-66-HBA as heterocatalyst for epoxide cycloaddition with CO2. Compared to UiO-66, the optimal UiO-66-HBA0.2 displayed outstanding activity for epichlorohydrin cycloaddition, with 96.03 % cyclocarbonate yield under 0.1 MPa CO2 at 70 ℃. The great activity of UiO-66-HBA0.2 was attributed to the synergistic cooperation of Lewis base offered by HBA moiety and Lewis acid originated from Zr6 clusters, which was affirmed by NH3/CO2-temperature-programmed desorption experiments and CO2 adsorption isotherms. Moreover, UiO-66-HBA0.2 exhibited excellent stability and great substrate compatibility. In addition, a possible mechanism for catalyzing CO2 conversion into cyclocarbonate was suggested. This study provides an effective way to design functionalized MOFs-based heterocatalysts for CO2 utilization.

Enhanced oil recovery and carbon sequestration in low-permeability reservoirs: Comparative analysis of CO2 and oil-based CO2 foam

Excessive CO2 emissions contribute to global climate change thus mandating effective methods for CO2 utilization and sequestering. In this study, one-dimensional flow simulation experiments on CO2 flooding, CO2 Huff-n-Puff, oil-based CO2 foam flooding, and oil-based CO2 foam Huff-n-Puff are conducted using low-permeability sandstone cores modeled after the Q131 block in Liaohe Oilfield, characterized by porosity ranging from 15% to 20% and permeability between 25 mD to 35 mD. Low permeability reservoirs are rich in oil resources and may effectively sequester CO2. Parameters pertaining to oil and gas production and carbon storage are collected. Nuclear magnetic resonance (NMR) is employed to determine the spatial variation of oil saturation in the cores. The experimental results show 8.03% and 41.21% increase in oil recovery factor by foam flooding and foam Huff-n-Puff relative to CO2 as the recovery agent. Moreover, NMR analysis confirms lower residual oil saturation in core samples using foam, suggesting better displacement agent. Oil-based CO2 foam recovery contributed to effective carbon sequestration, with carbon storage increasing by 34.24% and 315% relative to CO2 flooding and CO2 Huff-n-Puff, respectively. CO2 storage mechanisms for oil-based CO2 foam recovery method are detailed.

Simultaneous Photocatalytic CO 2 Reduction andH 2 O Oxidationunder Non-sacrificial Ambient Conditions.

The utilization ofCO2,H2O,and solar energy is regarded as a sustainable route for converting CO2into chemical feedstocks,paving the way for carbon neutrality and reclamation. However, the simultaneous photocatalytic CO2reduction andH2O oxidationunder non-sacrificial ambient conditions isstillasignificant challenge. Researchers have carried out extensive exploration and achieved dramaticdevelopmentsin this area. In this review, we firstprimarily elucidate the principles oftwo half-reactionsinthe photocatalytic conversion of CO2with H2O, i.e., CO2reductionby the photo-generated electrons and protons, andH2O oxidationby the photo-generated holeswithout sacrificial agents. Subsequently,the strategies to promote two half-reactions are summarized, including the vacancy/facet/morphologydesign, adjacent redox siteconstruction, and Z-scheme heterojunctiondevelopment. Finally, we present the advancedin situ characterizations and future perspectives inthis field. This review aimsto providefresh insights intoeffectivelysimultaneous photocatalytic CO2reduction andH2O oxidation under non-sacrificial ambient conditions.

CO2 utilization and on-purpose ethylene production: a chemical looping approach

CO2-assisted ethane dehydrogenation (CO2-ODHE) is a promising carbon atom economy process for upgrading CO2 to CO in tandem with C2H6 to C2H4 conversion. Iron oxide-based materials are selective for on purpose ethylene production through CO2-ODHE. The feed admission mode was found to play an important role on catalytic performance. Alternating C2H6 (reduction step) and CO2 (oxidation step) feedstock to a fixed bed reactor (chemical looping concept, CO2-ODHE-CL) attained constant ethane and CO2 conversion per step at 600oC, equal to ~17.6%, while C2H4 selectivity during the reduction step was ~75%. The lattice oxygen mobility is a descriptor for the materials used during the CO2-ODHE-CL, since low mobility resulted in an increased C-H bond scission selectivity, i.e., C2H4 production, during the reduction step. Temperature programmed 18O2 isotope exchange experiments, along with temperature programmed H2 – reduction, were employed to exemplify the latter statement, investigating the lattice oxygen reactivity of the examined materials and the mechanism through which the lattice oxygen is reacting. X-ray techniques (X-ray Diffraction, X-ray Raman Scattering Spectrometry, X-ray Absorption Spectrometry) along with structural modeling demonstrated that the formation of a spinel like arrangement between Mg and Fe, stabilized lattice oxygen and thus minimized the undesired C-C bond scission during the C2H6 step of CO2-ODHE-CL.

CO2 sequestration by indirect mineral carbonation of serpentine with (NH4)2SO4 as a recyclable extractant

Mineral carbonation with serpentine can offer a sustainable and safe process option for simultaneous CO2 emission reduction and utilization of nature mineral. In this study, a sustainable process for CO2 mineral sequestration was proposed by using serpentine and ammonium sulfate as feedstocks. The mixture of feedstocks was subjected to roasting with temperature ranging from 390°C to 480°C, converting magnesium into the corresponding sulfate. Then, water leaching was employed to dissolve the magnesium sulfate from the roasted samples. Finally, through a mineralization reaction, the corresponding magnesium bicarbonate was generated after sequestrating CO2. Under the optimal roasting-leaching conditions, i.e. roasting temperature of 420ºC, roasting time of 2 hours, and mass ratio of ammonium sulfate/serpentine of 3; leaching temperature of 80ºC, leaching time of 1 hour, and a liquid-to-solid ratio of 1, the magnesium extraction efficiency reached 76 %. Thermodynamics and experimental results demonstrated that during the sulfation roasting process, the products generated during roasting, magnesium sulfate and silicon dioxide, adhered to the surface of the serpentine, thus inhibiting the mass transfer process and impeding the progress of the reaction. However, the liquid-solid reaction facilitated by molten ammonium sulfate and the gas-solid reaction provided by the decomposition of ammonium salts into SO2 played a promoting role in the sulfation roasting reaction. The carbonation of sulfated serpentine results indicated that the optimal CO2 storage capacity can reach 204 kg/t serpentine.