N-doped Porous Carbon Derived from the Pyrolysis of a Polydopamine-coated Hypercross-linked Polymer for Enhanced CO2 Adsorption.

Porous carbon materials can simultaneously capture and convert carbon dioxide, helping to reduce greenhouse gas emissions and using carbon dioxide as a feedstock for the production of valuable chemicals or fuel. In this work, a series of N-doped porous carbons (PDA@HCP(x:y)-T) was prepared; the CO2 adsorption capacity of the prepared PDA@HCP(x:y)-T was enhanced by coating polydopamine (PDA) on a hypercross-linked polymer (HCP) and then adjusting the mass ratio of PDA to HCP and the carbonization temperature. The results showed that the prepared PDA@HCP(1:1)-850 exhibited a high CO2 adsorption capacity due to abundant micropores (0.6762 cm3/g), a high specific surface area (1220.8 m²/g), and moderate surface nitrogen content (2.75%). Notably, PDA@HCP(1:1)-850 exhibited the highest CO2 uptake of 6.46 mmol/g at 0 °C and 101 kPa. Critically, these N-doped porous carbons can also be used as catalysts for the reaction of CO2 with epichlorohydrin to form chloropropylene carbonate, with chloropropylene carbonate yielding up to 64% and selectivity of the reaction reaching 94%. As a result, these N-doped porous carbons could serve as potential candidates for CO2 capture and conversion due to their high reactivity, excellent CO2 uptake, and good catalytic performance.

Regulation of Ir Dopant in Mo Oxides by Flame Spray Pyrolysis for Efficient CO2 Hydrogenation.

Mo carbide is recognized as one of the most promising catalyst for CO2 utilization via reverse water-gas shift (RWGS). However, it always suffered from low processing capacity, undesired products and deactivation. Herein, an Ir modified MoO3 synthesized by the flame spray pyrolysis (FSP) method exhibits higher reaction rate (63.0 gCO2·gcat-1·h-1) compared to the one made by traditional impregnation method (45.8 gCO2·gcat-1·h-1) over the RWGS reaction at 600°C. The distinguishing feature between the two catalysts lies in the chemical state and space distribution of Ir species. Ir species predominated in the bulk phase of MoO3 during the quenching process of the FSP method and were mainly in the metallic states, which revealed by X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (ToF-SIMS) characterizations. In contrast, the Ir introduced via impregnation method were mainly on the surface of MoO3 and in oxidized state. The regulation of Ir dopant in MoO3 catalyst by different methods determines the carbonization process to Mo carbides, and thus affects the catalytic performance. This work sheds light on the superiority of the FSP method in synthesizing Mo oxides with heteroatoms and further creating an efficient Mo-based catalyst for CO2 conversion.

Critical impact of pressure regulation on carbon dioxide biosynthesis.

Carbon dioxide (CO2) biosynthesis is a promising alternative to traditional chemical synthesis. However, its application in engineering is hampered by poor gas mass transfer rates. Pressurization is an effective method to enhance mass transfer and increase synthesis yield, although the underlying mechanisms remain unclear. This review examines the effects of high pressure on CO2 biosynthesis, elucidating the mechanisms behind yield enhancement from three perspectives: microbial physiological traits, gas mass transfer and synthetic pathways. The critical role of pressurization in improving microbial activity and gas transfer efficiency is emphasized, with particular attention to maintaining pressure within microbial tolerance limits to maximize yield without compromising cell structure integrity.

Tandem Pt/TiO2 and Fe3C catalysts for direct transformation of CO2 to light hydrocarbons under high space velocity.

CO2 hydrogenation to hydrocarbons under high space velocity is crucial for industrial applications, but traditional Fe-based catalysts often suffer from the low activity and poor stability. Herein, we report a new tandem catalyst system combining Pt/TiO2 catalysts with Fe3C catalysts for the direct conversion of CO2 into C2-C4 hydrocarbons under high space velocity. The Pt/TiO2 component promotes *CO intermediate production with an enhanced Reverse Water-Gas Shift (RWGS) reaction efficiency, providing a highly reactive species for the Fe3C catalyst to achieve Fischer-Tropsch synthesis (FTS). By maximizing the contact interface between the Pt/TiO2 and Fe-based components through a granule mixing configuration, we achieve significant enhancements in both CO2 conversion rate (24.0 %) and C2-C4 hydrocarbons selectivity (51.1 %) under the gaseous hourly space velocity (GHSV) of 100000 mL gcat-1h-1. Besides, excellent stability is achieved by the tandem catalysts with continuous catalysis for up to 80 h without significant decrease in activity. Through modulation of the reduction states of iron oxide, we effectively tune the composition of Fe-based catalyst, thereby tailoring the product distribution. Through this work, we not only offer a promising avenue for reducing CO2 for efficient CO2 utilization but also highlight the importance of catalyst design in advancing sustainable chemical synthesis.

High-Entropy Metal-Organic Frameworks (HEMOFs): A New Frontier in Materials Design for CO2 Utilization.

High-entropy materials (HEMs) emerged as promising candidates for a diverse array of chemical transformations, including CO2 utilization. However, traditional HEMs catalysts are nonporous, limiting their activity to surface sites. Designing HEMs with intrinsic porosity can open the door toward enhanced reactivity while maintaining the many benefits of high configurational entropy. Here, a synergistic experimental, analytical, and theoretical approach to design the first high-entropy metal-organic frameworks (HEMOFs) derived from polynuclear metal clusters is implemented, a novel class of porous HEMs that is highly active for CO2 fixation under mild conditions and short reaction times, outperforming existing heterogeneous catalysts. HEMOFs with up to 15 distinct metals are synthesized (the highest number of metals ever incorporated into a single MOF) and, for the first time, homogenous metal mixing within individual clusters is directly observed via high-resolution scanning transmission electron microscopy. Importantly, density functional theory studies provide unprecedented insight into the electronic structures of HEMOFs, demonstrating that the density of states in heterometallic clusters is highly sensitive to metal composition. This work dramatically advances HEMOF materials design, paving the way for further exploration of HEMs and offers new avenues for the development of multifunctional materials with tailored properties for a wide range of applications.

CO2 hydrogenation to methanol over Pt functionalized Hf-UiO-67 versus Zr-UiO-67.

Sustainable methanol formation from CO2/H2 is potentially a key process in the post-fossil chemical industry. In this study, Hf- and Zr-based metal-organic framework (MOF) materials with UiO-67 topology, functionalized with Pt nanoparticles, have been tested for CO2 hydrogenation at 30 bar and 170-240°C. The highest methanol formation rate, 14 molmethanol molPt-1 h-1, was obtained over a Hf-based catalyst, compared with the maximum of 6.2 molmethanol molPt-1 h-1 for the best Zr-based analogue. However, changing the node metal did not significantly affect product distribution or apparent activation energy for methanol formation (44-52 kJ mol-1), strongly indicating that the higher activity of the Hf-based analogues is associated with a higher number of active sites. Both catalysts showed stable catalytic performance during testing under kinetic conditions, but the addition of 2 vol% water to the feed induced catalyst deactivation, in particular the Hf-MOFs. Interestingly, mainly methanol and methane formation rates decreased, while CO formation rates were less affected by deactivation. No direct correlation was found between catalytic stability and framework stability (crystallinity, specific surface area). Experimental and computational studies suggest that water adsorption strength to the MOF node may affect the relative catalytic stability of Hf-UiO-67-Pt versus Zr-UiO-67-Pt methanol catalysts.This article is part of the discussion meeting issue 'Green carbon for the chemical industry of the future'.

The Positional Effect of an Immobilized Re Tricarbonyl Catalyst for CO2 Reduction.

The storage of renewable energy through the conversion of CO2 to CO provides a viable solution for the intermittent nature of these energy sources. The immobilization of rhenium(I) tricarbonyl molecular complexes is presented through the reductive coupling of bis(diazonium) aryl substituents. The heterogenized complex was characterized through ultra-visible, attenuated total reflectance, infrared reflection absorption spectroscopy, and X-ray photoelectron spectroscopy to probe the electronic structure of the immobilized complex. In addition, studies of cyclic voltammetry, controlled potential electrolysis, and electrochemical impedance spectroscopy were conducted to examine the CO2 reduction activity. The structure and CO2 reduction performance were compared with a previously reported immobilized rhenium(I) tricarbonyl molecular complex to probe the effect of varying the tethering of the aryl substituent from the 5,5'-position to the 4,4'-position of the 2,2'-bipyridine backbone. The immobilized complex on carbon cloth at the 4,4'-position provided excellent selectivity (FECO > 99%) and maximum TONCO and TOFCO values of 3359 and 0.9 s-1, respectively, without the addition of a BroÌ·nsted acid source. A nonaqueous flow cell demonstrated the stability of this complex during a 5 h electrolysis. Tethering at the 4,4'-position, compared to the 5,5'-position, yielded lower overall activity for CO2 reduction and was attributed to the difference in growth morphology and formation of aggregations, due to Re-Re dimer formation and π-π stacking interactions within the metallopolymer matrix. For carbon cloth substrates, an optimized catalyst loading was determined to be 44.6 ± 11 nmol/cm2.

Surface-anchored N-based functional groups driven photoactivity of SrTiO3.

Surface modification, including the anchoring of functional groups is a popular method to increase the photocatalytic activity of semiconductor photocatalysts. These species can trap excited electrons, thus prolonging the life of the charge carriers. N-containing functional groups are suitable for this purpose due to their high electron density. Here, we report a facile synthesis method for preparing interfacial N-based functional groups-modified and nitrogen-doped SrTiO3 photocatalysts. Among the modified samples (with 0.42-11.14 at.% nominal nitrogen content), the one with 7.71 at.% nitrogen showed 6.4 times higher photooxidation efficiency for phenol and 2.2 times better photoreduction efficiency for CO2 conversion than the unmodified SrTiO3 reference. Characterization results showed that using a low amount of nitrogen source resulted in low but measurable nitrogen doping, which did not significantly affect the photocatalytic activity. The formation of surface amine groups was significant even at lower initial nitrogen concentrations, while higher amounts of nitrogen source gradually resulted in the incorporation of nitrogen in higher amounts. Surface amine groups decreased the recombination of charge carriers, resulting in increased photocatalytic activity.

Photocatalytic Synergy between α-Bi2O3 Nanosphere and Spindle MIL-88A for Gas-Phase CO2 Reduction.

Visible light-active photocatalysts play a crucial role in gas-phase photocatalytic CO2 reduction, offering significant potential for sustainable energy conversion. Herein, we present the synthesis of spindle-shaped Iron (Fe)-based metal-organic framework (MOF) MIL-88A, coupled with distinct α-Bi2O3 nanospheres. The α-Bi2O3/MIL88A heterostructure is formed by interacting opposite surface charges, enhancing visible-light absorption and efficient interfacial charge-carrier separation. Such low-cost photocatalysts have a 1.75 eV band gap and demonstrate enhanced efficacy in converting CO2 to CO, CH4, and H2 in water without using any sacrificial agents or noble metals compared to pristine MIL88A. In addition, in situ Electron Spin Resonance (ESR) analyses revealed that these unique catalysts combination promoted enhanced interfacial charge dynamics, creating efficient trapping sites for photogenerated carriers. Further, in-situ Diffuse Reflectance Infrared Fourier Transfer Spectroscopy (DRIFTS) investigation elucidates the plausible reaction mechanism and provides an effective methodology for catalyst screening for CO2 photoreduction. This study offers an effective approach for synthesizing the earth-abundant heterostructure from metal oxide and low-cost MOFs, enhancing photocatalytic activity for sustainable carbon dioxide conversion into invaluable chemicals.

Enhancing H2-driven CO2 biomethanation performance in bidirectional flow tidal bioreactor by reducing liquid film resistance and heterogeneity.

This study presents a bidirectional flow tidal bioreactor designed to enhance H2-driven CO2 biomethanation. The bioreactor alternated biofilms between immersion in nutrient solution and exposure to H2/CO2, creating alternating dry and wet states. This tidal operation minimized liquid film thickness during dry periods and ensured uniform nutrient distribution during wet periods. Bidirectional H2/CO2 supply was used to reduce biofilm thickness heterogeneity across the reactor height. CO2 biomethanation remained stable with an empty bed residence time of 9.7 min, achieving a methane (CH4) formation rate of 26.8 Nm3 CH4/(m3·d). The product gas contained 95.0 ± 2.5 % CH4, with a H2/CO2 conversion efficiency of 90.8 %. Tidal operation mitigated the buildup of dissolved and suspended organics, such as organic acids and detached biofilms. Dominant bacteria in biofilms included fermentative species like Petrimonas and H2-utilizing homoacetogens like Sporomusa. Enriched hydrogenotrophic methanogens, particularly Methanobacterium, were observed. Overall, this study highlights the bioreactor's effectiveness in improving CO2 biomethanation.

Non-thermal plasma-catalytic processes for CO2 conversion toward circular economy: fundamentals, current status, and future challenges.

Practical and energy-efficient carbon dioxide (CO2) conversion to value-added and fuel-graded products and transitioning from fossil fuels are promising ways to cope with climate change and to enable the circular economy. The carbon circular economy aims to capture, utilize, and minimize CO2 emissions as much as possible. To cope with the thermodynamic stability and highly endothermic nature of CO2 conversion via conventional thermochemical process, the potential application of non-thermal plasma (NTP) with the catalyst, i.e., the hybrid plasma catalysis process to achieve the synergistic effects, in most cases, seems to promise alternatives under non-equilibrium conditions. This review focuses on the NTP fundamentals and comparison with conventional technologies. A critical review has been conducted on the CO2 reduction with water (H2O), methane (CH4) reduction with CO2 to syngas (CO + H2), CO2 dissociation to carbon monoxide (CO), CO2 hydrogenation, CO2 conversion to organic acids, and one-step CO2-CH4 reforming to the liquid chemicals. Finally, future challenges are discussed comprehensively, indicating that plasma catalysis has immense investigative areas.

Anchoring MnWO4 Nanorods on LaTiO2N Nanoplates for Boosted Visible Light-Driven Overall CO2 Reduction.

The photocatalytic conversion of CO2 into hydrocarbon fuel holds immense potential for achieving a carbon closed loop and carbon neutrality. Developing efficient photocatalysts plays a pivotal role in enabling the widespread application of photocatalytic CO2 reduction on a large scale. Herein, a novel S-scheme MnWO4/LaTiO2N heterojunction composite is successfully synthesized by a hydrothermal method. This composite catalyst demonstrates excellent photocatalytic activity in the reduction of CO2 to CO and CH4 using water molecules as electron donors under visible light irradiation, and the optimized 30% MnWO4/LaTiO2N composite displays significantly enhanced CO and CH4 yields of 3.94 and 0.81 µmol g-1 h-1, respectively, and the corresponding utilized photoelectron number reaches 14.7 µmol g-1 h-1, which is approximately 7.7 and 12.9 times that of LaTiO2N and MnWO4. The enhancement in photocatalytic activity of the composites can be ascribed to the construction of an S-scheme heterojunction, which exhibits improved charge transfer dynamics, retains the strongest redox capacity, and effectively suppresses back reactions. In situ Fourier-transform infrared imaging provides evidence, to a certain extent, for the existence of a temporal gradient order in the generation of multiple products during the photocatalytic reduction of CO2.

Functional plasticity of HCO3- uptake and CO2 fixation in Cupriavidus necator H16.

Despite its prominence, the ability to engineer Cupriavidus necator H16 for inorganic carbon uptake and fixation is underexplored. We tested the roles of endogenous and heterologous genes on C. necator inorganic carbon metabolism. Deletion of ß-carbonic anhydrase can had the most deleterious effect on C. necator autotrophic growth. Replacement of this native uptake system with several classes of dissolved inorganic carbon (DIC) transporters from Cyanobacteria and chemolithoautotrophic bacteria recovered autotrophic growth and supported higher cell densities compared to wild-type (WT) C. necator in batch culture. Strains expressing Halothiobacillus neopolitanus DAB2 (hnDAB2) and diverse rubisco homologs grew in CO2 similarly to the wild-type strain. Our experiments suggest that the primary role of carbonic anhydrase during autotrophic growth is to support anaplerotic metabolism, and an array of DIC transporters can complement this function. This work demonstrates flexibility in HCO3- uptake and CO2 fixation in C. necator, providing new pathways for CO2-based biomanufacturing.

Exploring carbon-based Cu-ZnO catalyst and substitutes for enhanced selective methanol production from CO2: An integrated experimental and computational study.

Methanol, produced through the hydrogenation of carbon dioxide, is an essential intermediate compound that plays a crucial function in the production of various organic chemicals. Enhancing the design of copper-containing catalysts for the transformation of CO2 to methanol is a popular strategy in scientific literature, although challenges persist in advancing the efficiency of carbon dioxide transformation and the selectivity of methanol production. This research aims at creating CuZnO-M/rGO (M = Mg, Mn, and Cr) catalysts using an efficient method for selectively converting CO2 to methanol. By optimizing the operational parameters of this system, methanol productivity and CO2 conversion efficiency are enhanced. Under optimal conditions, a CO2 conversion rate of 23.5%, methanol selectivity of 90%, and a space-time yield of 0.47 gMeOH.gcat-1.h-1 were achieved with the CuZnO-MgO (5)/rGO catalyst. These levels were maintained over a 100-h period, demonstrating the stability of the catalyst system. These findings are highly consistent with the density functional theory (DFT) calculations, revealing that the CuZnO-MgO (5)/rGO catalyst possesses a -0.35 eV adsorption energy for CO2 and a favorable reaction pathway with the overpotential of 1.16 V towards methanol production emphasizing the high conversion and selectivity obtained.

Unmatched Redox Activity of the Palladium-Doped Indium Oxide Oxygen Carrier for Low-Temperature CO2 Splitting.

The chemical conversion of CO2 into value-added products is the key technology to realize a carbon-neutral society. One representative example of such conversion is the reverse water-gas shift reaction, which produces CO from CO2. However, the activity is insufficient at ambient pressure and lower temperatures (<600 °C), making it a highly energy-intensive and impractical process. Herein, we report indium oxide nanofibers modified with palladium catalysts that exhibit significantly potent redox activities toward the reduction of CO2 splitting via chemical looping. In particular, we uncover that the doped palladium cations are selectively reduced and precipitated onto the host oxide surface as metallic nanoparticles. These catalytic gems formed operando make In2O3 lattice oxygen more redox-active in H2 and CO2 environments. As a result, the composite nanofiber catalysts demonstrate the reverse water-gas shift reaction via chemical looping at record-low temperatures (≤350 °C), while also imparting high activities (CO2 conversion: 45%). Altogether, our findings expand the viability of CO2 splitting at lower temperatures and provide design principles for indium oxide-based catalysts for CO2 conversion.

Carbon Dioxide Capture and Conversion Using Metal-Organic Framework (MOF) Materials: A Comprehensive Review.

The escalating threat of anthropogenic climate change has spurred an urgent quest for innovative CO2 capture and utilization (CCU) technologies. Metal-organic frameworks (MOFs) have emerged as prominent candidates in CO2 capture and conversion due to their large specific surface area, well-defined porous structure, and tunable chemical properties. This review unveils the latest advancements in MOF-based materials specifically designed for superior CO2 adsorption, precise separation, advanced photocatalytic and electrocatalytic CO2 reduction, progressive CO2 hydrogenation, and dual functionalities. We explore the strategies that enhance MOF efficiency and examine the challenges of and opportunities afforded by transitioning from laboratory research to industrial application. Looking ahead, this review offers a visionary perspective on harnessing MOFs for the sustainable capture and conversion of CO2.

Liquid Metal-Enabled Tunable Synthesis of Nanoporous Polycrystalline Copper for Selective CO2-to-Formate Electrochemical Conversion.

Copper-based catalysts exhibit high activity in electrochemical CO2 conversion to value-added chemicals. However, achieving precise control over catalysts design to generate narrowly distributed products remains challenging. Herein, a gallium (Ga) liquid metal-based approach is employed to synthesize hierarchical nanoporous copper (HNP Cu) catalysts with tailored ligament/pore and crystallite sizes. The nanoporosity and polycrystallinity are generated by dealloying intermetallic CuGa2 formed after immersing pristine Cu foil in liquid Ga in a basic or acidic solution. The liquid metal-based approach allows for the transformation of monocrystalline Cu to the polycrystalline HNP Cu with enhanced CO2 reduction reaction (CO2RR) performance. The dealloyed HNP Cu catalyst with suitable crystallite size (22.8 nm) and nanoporous structure (ligament/pore size of 45 nm) exhibits a high Faradaic efficiency of 91% toward formate production under an applied potential as low as -0.3 VRHE. The superior CO2RR performance can be ascribed to the enlarged electrochemical catalytic surface area, the generation of preferred Cu facets, and the rich grain boundaries by polycrystallinity. This work demonstrates the potential of liquid metal-based synthesis for improving catalysts performance based on structural design, without increasing compositional complexity.

New Insights for High-Throughput CO2 Hydrogenation to High-Quality Fuel.

In the case of CO2 thermal-catalytic hydrogenation, highly selective olefin generation and subsequent olefin secondary reactions to fuel hydrocarbons in an ultra-short residence time is a huge challenge, especially under industrially feasible conditions. Here, we report a pioneering synthetic process that achieves selective production of high-volume commercial gasoline with the assistance of fast response mechanism. In situ experiments and DFT calculations demonstrate that the designed NaFeGaZr presents exceptional carbiding prowess, and swiftly forms carbides even at extremely brief gas residence times, facilitating olefin production. The created successive hollow zeolite HZSM-5 further reinforces aromatization of olefin diffused from NaFeGaZr via optimized mass transfer in the hollow channel of zeolite. Benefiting from its rapid response mechanism within the multifunctional catalytic system, this catalyst effectively prevents the excessive hydrogenation of intermediates and controls the swift conversion of intermediates into aromatics, even in high-throughput settings. This enables a rapid one-step synthesis of high-quality gasoline-range hydrocarbons without any post-treatment, with high commercial product compatibility and space-time yield up to 0.9 kggasoline ⋅ kgcat -1 ⋅ h-1. These findings from the current work can provide a shed for the preparation of efficient catalysts and in-depth understanding of C1 catalysis in industrial level.

Direct conversion of CO2 to CH4 on Pd/graphdiyne single-crystalline.

A major impediment to the development of the efficient use of artificial photosynthesis is the lack of highly selective and efficient photocatalysts toward the conversion of CO2 by sunlight energy at room temperature and ambient pressure. After many years of hard work, we finally completed the synthesis of graphdiyne-based palladium quantum dot catalysts containing high-density metal atom steps for selective artificial photosynthesis. The well-designed interface structure of the catalyst is composed of electron-donor and acceptor groups, resulting in the obvious incomplete charge-transfer phenomenon between graphdiyne and plasmonic metal nanostructures on the interface. These intrinsic characteristics are the origin of the high performance of the catalyst. Studies on its mechanism reveal that the synergism between 'hot electron' from local surface plasmon resonance and rapid photogenerated carrier separation at the ohmic contact interface accelerates the multi-electron reaction kinetics. The catalyst can selectively synthesize CH4 directly from CO2 and H2O with selectivity of near 100% at room temperature and pressure, and exhibits transformative performance, with an average CH4 yield of 26.2 µmol g-1 h-1 and remarkable long-term stability.

Sustainable methanol production from carbon dioxide: advances, challenges, and future prospects.

The urgent need to address global carbon emissions and promote sustainable energy solutions has led to a growing interest in carbon dioxide (CO2) conversion technologies. Among these, the transformation of CO2 into methanol (MeOH) has gained prominence as an effective mitigation strategy. This review paper provides a comprehensive exploration of recent advances and applications in the direct utilization of CO2 for the synthesis of MeOH, encompassing various aspects from catalysts to market analysis, environmental impact, and future prospects. We begin by introducing the current state of CO2 mitigation strategies, highlighting the significance of carbon recycling through MeOH production. The paper delves into the chemistry and technology behind the conversion of CO2 into MeOH, encompassing key themes such as feedstock selection, material and energy supply, and the various conversion processes, including chemical, electrochemical, photochemical, and photoelectrochemical pathways. An in-depth analysis of heterogeneous and homogeneous catalysts for MeOH synthesis is provided, shedding light on the advantages and drawbacks of each. Furthermore, we explore diverse routes for CO2 hydrogenation into MeOH, emphasizing the technological advances and production processes associated with this sustainable transformation. As MeOH holds a pivotal role in a wide range of chemical applications and emerges as a promising transportation fuel, the paper explores its various chemical uses, transportation, storage, and distribution, as well as the evolving MeOH market. The environmental and energy implications of CO2 conversion to MeOH are discussed, including a thermodynamic analysis of the process and cost and energy evaluations for large-scale catalytic hydrogenation.