Efficient Conversion Of CO2 Research Articles

A Comprehensive Review of CO2 Hydrogenation into Formate/Formic Acid Catalyzed by Whole Cell Bacteria.

The increasing levels of carbon dioxide (CO2) in the atmosphere, primarily due to the use of fossil fuels, pose a significant threat to the environment and necessitate urgent action to mitigate climate change. Carbon capture and utilization technologies that can convert CO2 into economically valuable compounds have gained attention as potential solutions. Among these technologies, biocatalytic CO2 hydrogenation using bacterial whole cells shows promise for the efficient conversion of CO2 into formate, a valuable chemical compound. Although it was discovered nearly a century ago, comprehensive reviews focusing on the utilization of whole-cell bacteria as the biocatalyst in this area remain relatively limited. Therefore, this review provides an analysis of the progress, strategies, and key findings in this field. It covers the use of living cells, resting cells, or genetically modified bacteria as biocatalysts to convert CO2 into formate, either naturally or with the integration of electrochemical and protochemical techniques as sources of protons and electrons. By consolidating the current knowledge in this field, this review article aims to serve as a valuable resource for researchers and practitioners interested in understanding the recent progress, challenges, and potential applications of bacterial whole cell catalyzed CO2 hydrogenation into formate.

Exploring the CO2 conversion activated by the dielectric barrier discharge plasma assisted with photocatalyst via machine learning

DBD plasma assisted with halide perovskite photocatalysts is very attractive for the conversion of CO2 into high value-added products under mild conditions. However, it is still challenging to further effectively improve the corresponding CO2 conversion efficiency due to the consumption of time, materials, equipments via traditional experimental approach. In this paper, we simulate the CO2 conversion process under the DBD plasma assisted with different photocatalysts by machine learning. The process conditions and material parameters were selected as the feature variables of the machine learning model, and all the features were screened by combining Pearson's correlation coefficient and MIR ranking. The regression algorithms were evaluated using K-fold cross-validation combined with the coefficient of determination (R2), while SVR and BPANN with the best prediction performance for CO2 conversion ratio and energy efficiency were selected to establish the prediction models. In order to increase the accuracy of predictions, the hyperparameters of these two base models were improved using genetic algorithm, particle swarm optimization and Bayesian optimization. The R2 of the GA-SVR-CO2 and Bayesian-BPANN-EE reached 0.8960 and 0.9679 for the testing sets, respectively, and their practical applications were successfully verified. In addition, the effects of feature parameters on the conversion efficiency were revealed by SHAP. SEI scatter plots and Spearman correlation coefficient have been used for correlation analysis to better explore the correlation between machine learning models and experiments. This work brings new insights into the contributions of multiple parameters in the plasma system assisted with photocatalyst for efficient conversion of CO2.

The effects of different functional groups in Ni3-cluster MOFs on the efficient capture and transformation for flue gas CO2

As the greenhouse effect continuous increasing, the efficient CO2 capture and conversion into high-value fine chemicals have been necessary and meaningful. However, the CO2 coupling reaction always requires harsh catalytic reaction conditions and focuses on pure CO2 gas. Herein, three nickel-cluster metal-organic frameworks (MOFs) with different functional groups on the bridging-ligands have been synthesized and characterized structurally, presenting unique cages and channels architectural features. Catalytic investigations demonstrated that the amino-functionalized MOFs as a catalyst {[H2N(CH3)2]2[Ni3(µ3-O)(XN)(BDC-NH2)3∙7DMF}n (Ni3-NH2, XN = 6′′-(pyridin4-yl)-4,2′′:4′′,4′′′-terpyridine, H2BDC-NH2 = 2-aminoterephthalic acid) owns higher catalytic activity (96 %) than the other two in the CO2 transformation reaction with aziridine into oxazolidinones under 0.5 MPa within 4 h. Moreover, Ni3-NH2 can be reused at least ten times without significant catalytic activity loss under mild condition. Importantly, Ni3-NH2 catalyst still can be applicable to the simulating flue gas with 15 % CO2 as carbon source. The mechanism has been further revealed by NMR, FT-IR and DFT calculations, in which the Ni-site and the amino group can synergistically activate the substrate and CO2 molecule. This work has enriched the species of cluster-based MOFs and investigated the influence of characteristic functional groups on the catalytic activity deeply.

Dual Metallosalen-based Covalent Organic Frameworks for Artificial Photosynthetic Diluted CO2 Reduction.

Directly converting CO2 in flue gas using artificial photosynthetic technology represents a promising green approach for CO2 resource utilization. However, it remains a great challenge to achieve efficient reduction of CO2 from flue gas due to the decreased activity of photocatalysts in diluted CO2 atmosphere. Herein, we designed and synthesized a series of dual metallosalen-based covalent organic frameworks (MM-Salen-COFs, M: Zn, Ni, Cu) for artificial photosynthetic diluted CO2 reduction and confirmed their advantage in comparison to that of single metal M-Salen-COFs. As a results, the ZnZn-Salen-COF with dual Zn sites exhibits a prominent visible-light-driven CO2-to-CO conversion rate of 150.9 μmol g-1 h-1 under pure CO2 atmosphere, which is ~6 times higher than that of single metal Zn-Salen-COF. Notably, the dual metal ZnZn-Salen-COF still displays efficient CO2 conversion activity of 102.1 μmol g-1 h-1 under diluted CO2 atmosphere from simulated flue gas conditions (15% CO2), which is a record high activity among COFs- and MOFs-based photocatalysts under the same reaction conditions. Further investigations and theoretical calculations suggest that the synergistic effect between the neighboring dual metal sites in the ZnZn-Salen-COF facilitates low concentration CO2 adsorption and activation, thereby lowering the energy barrier of the rate-determining step.

Dual Metallosalen‐based Covalent Organic Frameworks for Artificial Photosynthetic Diluted CO2 Reduction

Directly converting CO2 in flue gas using artificial photosynthetic technology represents a promising green approach for CO2 resource utilization. However, it remains a great challenge to achieve efficient reduction of CO2 from flue gas due to the decreased activity of photocatalysts in diluted CO2 atmosphere. Herein, we designed and synthesized a series of dual metallosalen‐based covalent organic frameworks (MM‐Salen‐COFs, M: Zn, Ni, Cu) for artificial photosynthetic diluted CO2 reduction and confirmed their advantage in comparison to that of single metal M‐Salen‐COFs. As a results, the ZnZn‐Salen‐COF with dual Zn sites exhibits a prominent visible‐light‐driven CO2‐to‐CO conversion rate of 150.9 μmol g−1 h−1 under pure CO2 atmosphere, which is ~6 times higher than that of single metal Zn‐Salen‐COF. Notably, the dual metal ZnZn‐Salen‐COF still displays efficient CO2 conversion activity of 102.1 μmol g−1 h−1 under diluted CO2 atmosphere from simulated flue gas conditions (15% CO2), which is a record high activity among COFs‐ and MOFs‐based photocatalysts under the same reaction conditions. Further investigations and theoretical calculations suggest that the synergistic effect between the neighboring dual metal sites in the ZnZn‐Salen‐COF facilitates low concentration CO2 adsorption and activation, thereby lowering the energy barrier of the rate‐determining step.

Triazine- and amino-functionalized poly(ionic liquid) heterogeneous catalyst for efficient CO2 conversion under mild conditions

The efficient conversion of atmospheric CO2 into high value-added chemicals remains a persistent challenge. In this study, a novel strategy for the fabrication of triazine- and amino-functionalized poly(ionic liquid)s (PILs) was reported. By virtue of the rich nitrogen species, the newly-developed PILs possessed great potential in CO2 conversion to produce high-value chemicals. The systematic investigation illustrated that rich-nitrogen PILs could promote the cycloaddition reaction of CO2 and epoxides through the intramolecular synergy of multiple active sites. Excellent conversion and selectivity were achieved under the mild conditions without any co-catalysts and solvents. In addition, PIL heterogeneous catalysts could be easily recovered and reused at least several times without obvious loss in activity. The density functional theory calculation demonstrated that the superior catalytic activity of rich nitrogen PILs was attributed to the synergistic effect of hydrogen bond donor and triazine ring in the catalytic process. Our finding thus presents a versatile platform for fabricating multi-functional heterogeneous catalysts for efficient CO2 conversion.

The embedding of 1,8-diazabicyclo[5.4.0]undec-7-ene into hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure

The preparation of cyclic carbonates via CO2 cycloaddition reaction was crucial for the lithium industry. Herein, a series of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) based hyper-crosslinked ionic polymers with different ionic site densities were prepared by simultaneously Friedel-Crafts alkylation and quaternization reactions. The obtained P[DBU]DCX(1:1) with a high ionic site density (1.45 mmol g−1), prepared by the equimolar ratio of 1,8-diazabicyclo[5.4.0]undec-7-ene and α,α′-dichloro-p-xylene, exhibiting excellent catalytic performance with a chloropropylene carbonate (CPC) yield of 98.8 % and selectivity of 99.3 % at atmospheric pressure. Meanwhile, the conversion capacity was comparable with other catalysts. Moreover, the CO2 cycloaddition reaction over P[DBU]DCX(1:1) catalyst followed pseudo-first-order kinetics, and the activation energy (Ea) was obtained to be 28.7 kJ/mol by performing kinetic experiments at different temperatures. In addition, it also had a good reusability and universality for different epoxides. The synergistic effects of abundant quaternary nitrogen cations derived from DBU and chlorine anions on the activation of CO2 and epoxide were explored based on density functional theory calculation. This study offers a new approach for the design and application of hyper-crosslinked ionic polymers for efficient CO2 conversion at atmospheric pressure.

Au Cluster-Nanoparticle Dual Coupling for Photocatalytic CO2 Conversion.

CO2-selective photoreduction to value-added products is ideal, but its practical application suffers from weak photogenerated carrier separation and insufficient multielectron transport. Herein, we constructed the tricomponent AuNPs@SnO2-AuNCs hybrid by decorating Au nanoclusters (AuNCs) on the Au nanoparticle (AuNPs)@SnO2 core-shell structure. AuNC-NP dual coupling endowed AuNPs@SnO2-AuNCs with an excellent CO yield of 64.8 μmol g-1 h-1 during CO2 photoreduction, which was higher than the role of separate application of AuNCs (25.3 μmol g-1 h-1) and AuNPs (16.0 μmol g-1 h-1). It was mainly attributed that the coaction of AuNPs and AuNCs not only enhanced the visible light absorption capacity but also improved the photogenerated carrier separation/migration. As a result, the electron-rich AuNCs induced from plasmonic AuNPs and photoexcited SnO2 promoted the photocatalytic CO2-to-CO performance. This work provides a new perspective to design multicomponent photocatalysts for highly efficient CO2 conversion.

Post-crosslinking knitting strategy for triazine-functionalized ionic hypercrosslinked polymers: Enhanced CO2 adsorption and conversion

Pore engineering has gained significant recognition as a pivotal strategy to tailor the structure and functionality of porous materials. In this study, a post-crosslinking knitting strategy was employed to fabricate a series of triazine-functionalized ionic hypercrosslinked polymers (IHCPs) using low specific surface area ionic polymers as precursors and external crosslinkers α,α′-dichloro-p-xylene (DCX) and α,α′-dibromo-p-xylene (DBX) through the Friedel Crafts alkylation reaction. This post-crosslinking knitting methodology increases the specific surface area of the resulting IHCPs, leading to enhanced CO2 adsorption capabilities (reaching 1.92 mmol·g−1 at 1 bar and 273 K), enhanced a remarkable 5.6-fold increase in CO2 uptake compared to the original ionic polymers. Of particular interest, inclusion of –NH– groups in PTA-2-DBX exhibits a synergistic catalytic effect facilitated by hydrogen bonding interactions that enable efficient conversion of CO2 into various cyclic carbonates under solvent- and cocatalyst-free conditions with yields exceeding 99 %. Furthermore, PTA-2-DBX demonstrates excellent recyclability while maintaining its activity even after five consecutive cycles. This study offers an effective approach for modulating pores in ionic polymers while highlighting the promising applications of triazine-functionalized IHCPs as dual-functional materials for both CO2 capture and conversion.

Atmosphere engineering of metal-free Te/C3N4 p-n heterojunction for nearly 100% photocatalytic converting CO2 to CO

Carbon nitride (CN)-based heterojunction photocatalysts hold promise for efficient carbon dioxide (CO2) reduction. However, suboptimal production yields and limited selectivity in CO2 conversion pose significant barriers to achieving efficient CO2 conversion. Here, we present the construction of a p-n heterojunction between ultrasmall Te NPs and CN nanosheet using a novel tandem hydrothermal-calcination synthesis strategy. Through ammonia-assisted calcination, ultrasmall Te NPs are grown in-situ on the CN nanosheets’ surface, resulting in the generation of a robust p-n heterojunction. The synthesized heterojunction exhibits increased specific surface area, reinforced visible light absorption, intensive CO2 adsorption capacity, and efficient charge transfer. The optimum Te/CN-NH3 demonstrates superior photocatalytic CO2 reduction activity and durability, with nearly 100 ​% selectivity for CO and a yield as high as 92.0 ​μmol ​g−1 ​h−1, a fourfold increase compared to pure CN. Experimental and theoretical calculations unravel that the strong built-in electric field of the Te/CN-NH3 p-n heterojunction accelerates the migration of photogenerated electrons from Te NPs to the N site on CN nanosheets, thereby promoting CO2 reduction. This study provides a promising material design approach for the construction of high-performance p-n heterojunction photocatalysts.

Monolithic Nitrogen-Doped Carbon Electrode with Hierarchical Porous Structure for Efficient Electrochemical CO2 Reduction.

N-doped carbon materials have garnered extensive development in electrochemical CO2 reduction due to their abundant sources, high structural plasticity, and excellent catalytic performance. However, the use of powder carbon materials for electrocatalytic reactions limits their current density and mechanical strength, which pose challenges for industrial applications. In this study, we synthesized a monolithic N-doped carbon electrode with high mechanical strength for efficient electrochemical reduction of CO2 to CO through a simple pyrolysis method, using phenolic resin as the precursor and ZIF-8 as the sacrificial template. At 900 °C, the decomposition of ZIF-8 and the volatilization of Zn atoms promote the formation of a hierarchical porous structure in the carbon matrix, characterized by macropores with extended mesoporous channels. Simultaneously, N active species derived from ZIF-8 are effectively generated around the pores and fully exposed. The efficient mass transfer facilitated by the hierarchical porous structure and high activity of exposed nitrogen species enables efficient conversion of CO2 to CO. When the ZIF-8 content is 30%, the catalyst achieves a Faradaic efficiency of 88.9% for CO at a low potential of -0.7 V (vs RHE), with a CO production rate of 244.05 μmol h-1 cm-2. After 50 h of potentiostatic electrolysis, the current density and FECO remain stable. This work not only provides a strategy for the synergistic effects of hierarchical porous structures and nitrogen doping but also offers an effective method to avoid using powder binders and prepare integrated, stable monolithic electrodes.

Li/Na/K carbonate solar salts for enhanced and integrated carbon capture and utilization via reverse water gas shift (ICCU-RWGS)

This study introduces a novel ICCU-RWGS process using Li, Na, and K carbonates mixed with boric acid as dual functional materials, enhancing CO2 capture and conversion without traditional CaO adsorbents. These molten salts, compatible with solar energy systems, enable efficient integration with CSP, storing heat from CO2 capture for utilization. The addition of boric acid significantly boosts CO2 uptake and conversion, achieving 2.0 mmol, 1.1 mmol, and 1.3 mmol CO2 uptake with conversion of 51.1 %, 58.3 %, and 57.6 % over three cycles, respectively. A 10-cycle test confirmed stable performance, with conversion rates between 53.0 % and 58.7 %. Characterization techniques (XRD, SEM, TEM, XPS, in-situ DRIFTS) revealed new borate phases after CO2 capture. TG-DSC analysis showed exothermic peaks during CO2 capture and RWGS stages, indicating that molten salt has the potential to generate heat for CSP systems, thus offering efficient CO2 conversion and sustainable energy recovery.

Highly efficient hydrogenation of CO2 to heavy hydrocarbons via NaFeGa catalysts

Transforming CO2 into heavy hydrocarbons via thermal catalytic hydrogenation has garnered interest for its potential to address resource shortages and reduce atmospheric CO2. In this research, NaFeGa catalysts enriched with Ga additives were synthesized by the coprecipitation method. Various characterization techniques, including Mössbauer spectroscopy, were employed alongside reverse water-gas shift and Fischer-Tropsch synthesis experiments to elucidate the Fe-Ga interaction. This interaction effectively modulated the ratio of active sites Fe5C2 and enhanced CO species adsorption. The Ga additive's anti-hydrogenation effect limited intermediate hydrogenation, leading to increased carbon-hydrogen product yields. The catalyst underwent direct hydrogenation of CO2 under high throughput conditions (space velocity of 50,000 h−1), resulting in efficient CO2 conversion as well as remarkable heavy hydrocarbon selectivity. The catalyst demonstrated a remarkable heavy hydrocarbon space-time yield (STY) of 1460.2 g·kgcat−1·h−1, surpassing the threshold for commercial viability and offering a promising solution for large-scale production of liquid fuels from CO2.

Stable hierarchical ionic liquid nanochannels for highly efficient CO2 adsorption, separation and conversion

Constructing stable nanochannels and nanoconfined environments for ionic liquids holds significant application value in gas separation, ion channels, and related fields. The functional polyionic liquid synthesized in this study exhibits a controllable assembly structure and demonstrates liquid crystal properties. Through heating and water treatment, the polyionic liquids crosslink to form multi-hierarchical nanopores, including sub-nanochannels with pore sizes similar to CO2, without the need for a catalyst. The specific surface area and pore size of the polyionic liquid network (PILC) were adjusted by regulating the self-assembly of polyionic liquids in water. The unique PILC, combining ionic liquid nanopores and liquid crystal structure properties, shows high CO2 adsorption performance and excellent CO2/N2 selectivities, surpassing commonly reported ionic liquid porous materials. Furthermore, PILC-2 exhibits good catalytic performance for CO2 cycloaddition, and its catalytic activity and selectivity did not significantly decrease after five cycles. This study successfully introduces hierarchical ionic liquid nanochannels into porous networks without involving any inorganic ordered nanomaterials. This provides a simple and effective approach for the highly selective adsorption and separation of CO2, as well as for the preparation of catalytic materials.

Sustainable repurpose of waste melamine foam into bifunctional catalysts for efficient CO2 capture and conversion

Global climate change has driven the scientific community to improve the utilization of a critical C1 resource carbon dioxide (CO2) through carbon capture utilization (CCU) technology. The cycloaddition of CO2 with epoxides provides perfect atom economy and economic feasibility to produce versatile cyclic carbonates used in various industries. However, the stable nature of CO2 and epoxides requires highly active catalysts. In this work, the repurpose of nitrogenous waste melamine foams (MFs) as high-performance catalysts for the cycloaddition of CO2 was explored. The pyrolyzed MF was modified with Cu to prepare a series of acid-base bifunctional porous catalysts (MFC-X-Cu). The results demonstrate that the acid-base synergy of the MFC-X-Cu catalysts increases the efficiency of the cycloaddition of various epoxides, yielding target products at 96–99% under mild conditions. Moreover, the characterization results revealed that the superior performance of MFC-X-Cu stems from its hollow structure and acid-base synergy, which are derived from nitrogen species in the repurposed MF and the post-modified copper component. The catalyst maintained consistent catalytic efficiency over five cycles, highlighting its strong recyclability. This work presents an eco-friendly and sustainable approach towards carbon neutrality by utilizing modified waste materials for CO2 conversion into high-value chemicals.

Photocatalytic performance of metal poly(heptazine imide) for carbon dioxide reduction

Poly(heptazine imide) (PHI), a carbon nitride polymer, is a highly efficient visible-light-driven photocatalytic material. We aimed to improve its photocatalytic performance for CO2 conversion. We prepared M-PHIs by encapsulating different metals (M = K, Li, Rb, and Na) and H-PHIs, in which the metal of each M-PHI was ion-exchanged with a proton. We evaluated their photocatalytic activities for CO2 conversion and found that Na-PHI and H-PHI, prepared from Na-PHI (H-PHI(NaCl)), showed more than twice the CO production efficiency of melon and other PHIs.The high CO production efficiency of Na-PHI and H-PHI(NaCl) was attributed to their extremely smaller particle size compared with those of the other PHIs. By closely examining the synthesis conditions of Na-PHI, we have identified a method to intentionally synthesize M-PHI with small particle size. These results provide a new strategy for highly efficient CO2 conversion using PHI.

Advancements in covalent organic framework‐based nanocomposites: Pioneering materials for CO2 reduction and storage

AbstractThe persistent increase in atmospheric carbon dioxide (CO2) concentration poses a significant contemporary challenge. Contemporary chemistry is heavily focused on sustainable solutions, particularly the photo‐/electrocatalytic reduction of CO2 and its utilization for energy storage. Despite promising prospects, efficient chemical CO2 conversion faces obstacles such as ineffective CO2 uptake/activation and catalyst mass transport. Covalent organic frameworks (COFs) have emerged as potential catalysts due to their precise structural design, functionalizable chemical environments, and robust architectures. COF‐based materials, especially those incorporating diverse active sites like single metal sites, metal nanoparticles, and metal oxides, hold promise for CO2 conversion and energy storage. This review sheds light on CO2 photoreduction/electroreduction and storage in Li‐CO2 batteries catalyzed by COF‐based composites, focusing on recent advancements in integrating COFs with nanoparticles for CO2 reduction. It discusses design principles, synthesis methods, and catalytic mechanisms driving the enhanced performance of COF‐based nanocomposites across various applications, including electrochemical reduction, photocatalysis, and lithium CO2 batteries. The review also addresses challenges and prospects of COF‐based catalysts for efficient CO2 utilization, aiming to steer the development of innovative COF‐based nanocomposites, thus advancing sustainable energy technologies and environmental stewardship. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Zinc-cluster-based MOF with super selective separation adsorption catalyzes direct chemical conversion of CO2 from quasi-polluted air

The CO2 in the atmosphere has a serious impact on the human living environment. Direct utilization of the discharged CO2 to produce useful chemicals is challenging due to the practical presence of mixed compositions and low concentrations for CO2. Metal-organic frameworks (MOFs) with high internal surface areas, porosity and open metal site potentially possess superior adsorption separation capacity for CO2 gas, and on this basis, it can be used as a catalyst to achieve efficient chemical conversion of CO2. We demonstrate the synthesis and characterization of MOF ([Zn4O(ntba)2]n, MOF 1, H3ntba=4,4',4''-nitrilotribenzoic acid) with excellent selective adsorption properties from quasi- polluted air (O2, N2, CO2, CH4) and as heterogeneous catalysts for direct efficient CO2 chemical conversion. Detailed structural analysis reveals show that zinc ions behave multiple open metal sites and two coordination modes in the polyhedral zinc clusters building unit forming a 3D porous network by polyhedral zinc clusters building unit. Thanks to its structural features, at the 273 K and 100kPa, due to the ideal specific surface area and porosity, MOF 1 have ideal adsorption-separation performance for CO2, its values of adsorption and separation ratio are 75.7 cm3g−1, 373(CO2/N2), 79(CO2/O2), 13(CO2/CH4), respectively. The cycloaddition catalytic reaction investigations show that MOF 1 can be employed as a highly efficient catalyst for converting CO2 with a yield of 78 %. The result of this experiment offers the potential to directly utilize low-concentration and mixed CO2 while avoiding the economic and environmental costs of obtaining purified CO2 feeds tocks.

Micro-Structure Engineering in Pd-InOx Catalysts and Mechanism Studies for CO2 Hydrogenation to Methanol.

Significant interest has emerged for the application of Pd-In2O3 catalysts as high-performance catalysts for CO2 hydrogenation to CH3OH. However, precise active site control in these catalysts and understanding their reaction mechanisms remain major challenges. In this investigation, a series of Pd-InOx catalysts were synthesized, revealing three distinct types of active sites: In-O, Pd-O(H)-In, and Pd2In3. Lower Pd loadings exhibited Pd-O(H)-In sites, while higher loadings resulted in Pd2In3 intermetallic compounds. These variations impacted catalytic performance, with Pd-O(H)-In catalysts showing heightened activity at lower temperatures due to the enhanced CO2 adsorption and H2 activation, and Pd2In3 catalysts performing better at elevated temperatures due to the further enhanced H2 activation. In situ DRIFTS studies revealed an alteration in key intermediates from *HCOO over In-O bonds to *COOH over Pd-O(H)-In and Pd2In3 sites, leading to a shift in the main reaction pathway transition and product distribution. Our findings underscore the importance of active site engineering for optimizing catalytic performance and offer valuable insights for the rational design of efficient CO2 conversion catalysts.

Molten Salt Synthesis of Ti3C2/Cu Cocatalyst for Enhanced TiO2 Photocatalytic CO2 Reduction

AbstractPhotocatalytic reduction of CO2 is considered as a crucial pathway towards achieving sustainable energy and environmental goals. Nonetheless, attaining efficient CO2 conversion poses significant challenges, primarily due to the slow dynamics of charge carriers and the high activation energy required to break C=O bonds. In this study, a novel strategy involving Lewis acid molten salt etching is investigated to engineer a titanium oxide (TiO2)‐based photocatalysts with dual electron transfer channels (i. e., Ti3C2/Cu), which targets the photoreduction of CO2 to CO and CH4. Thanks to the dual electron transfer channels presented in the cocatalysts (Ti3C2/Cu), in conjunction with the numerous heterogeneous interfaces between TiO2 and the Ti3C2/Cu cocatalysts, this hybrid catalyst not only reduces charge transfer resistance but also accelerates the dynamics of photogenerated charge carriers. Consequently, the TiO2/Ti3C2/Cu hybrid catalyst demonstrates an exceptional photocatalytic CO2 reduction rate of 13.67 μmol g−1 h−1, with a total utilized photoelectron number (UPN) of 102.34 μmol g−1 h−1. which is 3.99‐fold higher than that of unmodified TiO2. This research provides a new approach for the preparation of dual cocatalysts through a one‐step molten salt synthesis process.