Photochemical Reduction Of CO2 Research Articles

Site-Selective Zn-Metalation in Poly-Triphenyl Amine-based Porous Organic Polymer for Solid-Gas Phase CO2 Photoreduction.

Harvesting solar energy to produce value-added chemicals from carbon dioxide (CO2) presents a promising route for addressing the complexities of sustainable energy systems and environmental issues. In this context, the development of metal-coordinated porous organic polymers (POPs) offers a vital avenue for improving the photocatalytic performance of organic motifs. The current study presents a metal-integrated photocatalytic system (namely, Zn@BP-POP) developed via a one-pot Friedel-Crafts (F.C.) acylation strategy, for solid-gas phase photochemical CO2 reduction to CO (CO2RR). The postsynthetic incorporation of metal (Zn) active sites on the host polymeric backbone of BP-POP significantly influences the catalytic activity. Notably, Zn@BP-POP demonstrates good photocatalytic performance in the absence of any cocatalyst and photosensitizer yielding CO while impeding the competitive hydrogen evolution reaction (HER) from water. The experimental findings collectively propose that the observed catalytic activity and selectivity arise from the synergistic interplay between the singular zinc catalytic centers and the light-harvesting capacity of the highly conjugated polymeric backbone. Further, X-ray absorption spectroscopy (XAS) analysis has significantly highlighted the prominent role played by the ZnN2O4 single sites in the polymeric framework for activating the gaseous CO2 molecules. Further, time-dependent density functional theory (DFT) analysis also reveals the thermodynamic feasibility of CO2RR over HER under optimized reaction conditions. This work cumulatively presents an effective strategy to demonstrate the importance of metal-active sites and effectively establish their structure-activity relationship during photocatalysis.

Methane Formation Induced via Face-to-Face Orientation of Cyclic Fe Porphyrin Dimer in Photocatalytic CO2 Reduction.

Iron porphyrins are known to provide CH4 as an eight-electron reduction product of CO2 in a photochemical reaction. However, there are still some aspects of the reaction mechanism that remain unclear. In this study, we synthesized iron porphyrin dimers and carried out the photochemical CO2 reduction reactions in N,N-dimethylacetamide (DMA) containing a photosensitizer in the presence of 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as an electron donor. We found that, despite a low catalytic turnover number, CH4 was produced only when these porphyrins were facing each other. The close proximity of the cyclic dimers, distinguishing them from a linear Fe porphyrin dimer and monomers, induced multi-electron CO2 reduction, emphasizing the unique role of their structural arrangement in CH4 formation.

Superlative Porous Organic Polymers for Photochemical and Electrochemical CO2 Reduction Applications: From Synthesis to Functionality.

To mimic the carbon cycle at a kinetically rapid pace, the sustainable conversion of omnipresent CO2 to value-added chemical feedstock and hydrocarbon fuels implies a remarkable prototype for utilizing released CO2. Porous organic polymers (POPs) have been recognized as remarkable catalytic systems for achieving large-scale applicability in energy-driven processes. POPs offer mesoporous characteristics, higher surface area, and superior optoelectronic properties that lead to their relatively advanced activity and selectivity for CO2 conversion. In comparison to the metal organic frameworks, POPs exhibit an enhanced tendency toward membrane formation, which governs their excellent stability with regard to remarkable ultrathinness and tailored pore channels. The structural ascendancy of POPs can be effectively utilized to develop cost-effective catalytic supports for energy conversion processes to leapfrog over conventional noble metal catalysts that have nonlinear techno-economic equilibrium. Herein, we precisely surveyed the functionality of POPs from scratch, classified it, and provided a critical commentary of its current methodological advancements and photo/electrochemical achievements in the CO2 reduction reaction.

Ionic Liquid Modified Fe-Porphyrinic Metal-Organic Frameworks as Efficient and Selective Photocatalysts for CO2 Reduction.

Porphyrin-based metal-organic frameworks (MOFs) are ideal platforms for heterogeneous photocatalysts toward CO2 reduction. To further explore photocatalytic MOF systems, it is also necessary to consider their ability to fine-tune the microenvironments of the active sites, which affects their overall catalytic operation. Herein, a kind of ionic liquid (IL, here is 3-butyric acid-1-methyl imidazolium bromide, BAMeImBr) was anchored to iron-porphyrinic Zr-MOFs with different amounts to obtain ILx@MOF-526 (MOF-526 = Zr6O4(OH)4(FeTCBPP)3, FeTCBPP = iron 5,10,15,20-tetra[4-(4'-carboxyphenyl)phenyl]-porphyrin, x = 100, 200, and 400). ILx@MOF-526 series was designed to investigate the effects of the microenvironmental and electronic structural modification on the efficiency and selectivity of the photochemical reduction of CO2 after introducing IL fragments. Compared to parent MOF-526, the production and selectivity of CO were greatly improved in the absence of any photosensitizer under visible light by the ILx@MOF-526 series. Among them, the CO yield of IL200@MOF-526 was up to 14.0 mmol g-1 within 72 h with a remarkable CO selectivity of 97%, which is superior to that of MOF-526 without BAMeIm+ modification and other amounts of BAMeIm+ loaded. Furthermore, density functional theory calculations were performed to study the mechanism of the CO2 reduction.

Post-synthetic Metalation on the Ionic TiO2 Surface to Enhance Metal-CO2 Interaction During Photochemical CO2 Reduction.

During the photochemical CO2 reduction reaction, CO2 adsorption on the catalyst's surface is a crucial step where the binding mode of the [metal-CO2] adduct directs the product selectivity and efficiency. Herein, an ionic TiO2 nanostructure stabilized by polyoxometalates (POM), ([POM]x@TiO2), is prepared and the sodium counter ions present on the surface to balance the POMs' charge are replaced with copper(II) ions, (Cux[POM]@TiO2). The microscopic and spectroscopic studies affirm the copper exchange without altering the TiO2 core and weak coordination of copper (II) ions to the POMs' surface. Band structure analysis suggests the photo-harvesting efficiency of the TiO2 core with the conduction band edge higher than the reduction potential of CuII/I and multi-electron CO2 reduction potentials. Photochemical CO2 reduction with Cux[POM]@TiO2 results in 30 μmol gcat. -1 CO (79 %) and 8 μmol gcat -1 of CH4 (21 %). Quasi-in-situ Raman study provides evidence in support of CO2 adsorption on the Cux[POM]@TiO2 surface. 13C and D2O labeling studies affirm the {Cu-[CO2]-} adduct formation. Despite the photo-harvesting ability of Nax[POM]@TiO2 itself, the poor CO2 adsorption ability of sodium ions highlights the crucial role of copper ion CO2 photo-reduction. Characterization of the {M-[η2-CO2]-} species via surface tuning validates the CO2 activation and photochemical reduction pathway proposed earlier.

Tuning Photoredox Catalysis of Ruthenium with Palladium: Synthesis of Heterobimetallic Ru-Pd Complexes That Enable Efficient Photochemical Reduction of CO2.

New Ru-Pd heterobimetallic complexes were synthesized and structurally characterized utilizing 6,6″-bis(phosphino)-2,2':6',2″-terpyridine as a scaffold for the metal-metal bond. The dicationic Ru-Pd complex was found to exhibit high catalytic activity as a photocatalyst for photochemical reduction of CO2 to CO under visible light irradiation. This study established a new design of transition metal catalysts that tune photoredox catalysis with metalloligands.

Facile construction of double vacancy modified BiOBr/g-C3N4@Bi heterojunctions for effective photochemical CO2 reduction

Three different heterojunctions, BiOBr/g-C3N4, Bi/g-C3N4, and BiOBr/g-C3N4@Bi modified with carbon vacancies and/or oxygen vacancies, were first synthesized via a facile solvothermal approach by adjusting the ratio of Bi(NO3)3 5H2O with ethylene glycol (EG). The as-prepared heterojunctions were characterized by various modern analytical instruments, and their visible-light photocatalytic performance for CO2 conversion was evaluated. Our findings demonstrate that the ternary photocatalyst BiOBr/g-C3N4@Bi exhibits better activity toward visible-light-driven CO2 reduction than pristine g-C3N4 and its binary counterparts without hole scavengers, and its maximum CO yield (7.4 μmol h−1 g−1) is approximately four 4 times that of pure g-C3N4. This is attributed to the VO and VC defects, which enhance the photon absorption capacity. On the other hand, the g-C3N4 matrix exhibits strong interfacial interactions with BiOBr and metallic Bi, leading to an increase in the separation efficiency of the photoinduced carriers. In other words, the strong interfacial interactions among g-C3N4, BiOBr and metallic Bi, the vacancy defects VO and VC, and the metallic Bi particles cooperate to significantly improve the separation and transportation of the photoexcited charge carriers, thereby augmenting the CO2 photoreduction activity of the BiOBr/g-C3N4@Bi ternary heterojunction in the absence of a sacrificial agent. This approach based on facile solvothermal treatment has promising potential in fabricating highly efficient photocatalysts suitable for visible-light-driven CO2 reduction.

Non-trivial topological surface states regulation of 1 T-OsCoTe2 enables selective C―C coupling for highly efficient photochemical CO2 reduction toward C2+ hydrocarbons

Despite ongoing research, the rational design of non-trivial topological semimetal surface states for the selective photocatalytic CO2 conversion into valuable products remains full of challenges. Herein, we present the synthesis of lattice-matched 1 T-OsCoTe2 for the photoreduction upgrading of CO2 to tri-carbon (C3) alkane (propane, C3H8) by the integration of experimental work and theory prediction/calculation. Experimental studies suggested a high electron-based selectivity of 71.2 % for C3H8 and an internal quantum efficiency of 54.6 % at 380 nm. In-situ X-ray photoelectron spectroscopy and X-ray absorption fine structure spectroscopy demonstrated that Co and Os atoms coordinated with Te atoms enable an efficient Os―Te―Co electron transfer to activate the generation of *CH3, *CHOCO and *CH2OCOCO. Density functional theory calculations further confirmed Os―Te―Co electron bridging on the improved CO2 conversion kinetics. To our knowledge, this is the first report suggesting the role of Os atoms in accelerating the photocatalytic CO2 conversion activity of the topological semimetal 1 T-OsCoTe2.

Titanium carbide sealed cadmium sulfide quantum dots on carbon, oxygen-doped boron nitride for enhanced and durable photochemical carbon dioxide reduction

Despite great efforts that have been made, photocatalytic carbon dioxide (CO2) reduction still faces enormous challenges due to the sluggish kinetics or disadvantageous thermodynamics. Herein, cadmium sulfide quantum dots (CdS QDs) were loaded onto carbon, oxygen-doped boron nitride (BN) and encapsulated by titanium carbide (Ti3C2, MXene) layers to construct a ternary composite. The uniform distribution of CdS QDs and the tight interfacial interaction among the three components could be achieved by adjusting the loading amounts of CdS QDs and MXene. The ternary 100MX/CQ/BN sample gave a productive rate of 2.45 and 0.44 μmol g-1 h−1 for carbon monoxide (CO) and methane (CH4), respectively. This CO yield is 1.93 and 6.13 times higher than that of CdS QDs/BN and BN counterparts. The photocatalytic durability of the ternary composite is significantly improved compared with CdS QDs/BN because MXene can protect CdS from photocorrosion. The characterization results demonstrate that the excellent CO2 adsorption and activation capabilities of BN, the visible light absorption of CdS QDs, the good conductivity of MXene and the well-matched energy band alignment jointly promote the photocatalytic performance of the ternary catalyst.

Efficient Visible-Light-Driven Carbon Dioxide Reduction using a Bioinspired Nickel Molecular Catalyst.

Inspired by natural enzymes, this study presents a nickel-based molecular catalyst, [Ni‖(N2S2)]Cl2 (NiN2S2, N2S2=2,11-dithia[3,3](2,6)pyridinophane), for the photochemical catalytic reduction of CO2 under visible light. The catalyst was synthesized and characterized using various techniques, including liquid chromatography-high resolution mass spectrometry (LC-HRMS), UV-Visible spectroscopy, and X-ray crystallography. The crystallographic analysis revealed a slightly distorted octahedral coordination geometry with a mononuclear Ni2+ cation, two nitrogen atoms and two sulfur atoms. Photocatalytic CO2 reduction experiments were performed in homogeneous conditions using the catalyst in combination with [Ru(bpy)3]Cl2 (bpy=2,2'-bipyridine) as a photosensitizer and 1,3-dimethyl-2-phenyl-2,3-dihydro-1H-benzo[d]imidazole (BIH) as a sacrificial electron donor. The catalyst achieved a high selectivity of 89 % towards CO and a remarkable turnover number (TON) of 7991 during 8 h of visible light irradiation under CO2 in the presence of phenol as a co-substrate. The turnover frequency (TOF) in the initial 6 h was 1079 h-1, with an apparent quantum yield (AQY) of 1.08 %. Controlled experiments confirmed the dependency on the catalyst, light, and sacrificial electron donor for the CO2 reduction process. These findings demonstrate this bioinspired nickel molecular catalyst could be effective for fast and efficient photochemical catalytic reduction of CO2 to CO.

A Bio‐Inspired Bimetallic Fe−M Catalyst for Electro‐ and Photochemical CO2 Reduction

AbstractThe conversion of CO2 into fuels or commodity chemicals by electrochemical or photochemical reduction is a promising strategy to relieve the ongoing energy crisis and increasing environmental pollution. Inspired by naturally occurring bimetalloenzymes, we have designed hetero–bimetallic CO2 reduction catalysts (FeM) that involve linking an iron tetraphenylporphyrin (FeP) with a tripyridylamine (TPA) moiety, which provides a distal chelating site for Cu2+ or Zn2+. We found that the introduction of Cu2+ or Zn2+ to FeP greatly enhances its efficiency as a catalyst for the electrochemical reduction of CO2. To gain insights into the observed synergistic effect, we performed mechanistic studies together with density functional theory (DFT) calculations. Our results show that Cu2+ or Zn2+ activates CO2 towards reduction due to its Lewis acidity; it also functions as an oxo acceptor from CO2. FeM also functions as an efficient catalyst for the visible‐light‐driven reduction of CO2 using either [Ru(bpy)3] Cl2 or fac‐Ir(ppy)3 (where bpy=2,2’‐bipyridine, ppy=2‐phenylpyridine) as photosensitizer and 1,3‐dimethyl‐2‐phenyl‐2,3‐dihydro‐1H‐benzo[d] imidazole (BIH) as sacrificial reductant. Again, the catalytic efficiency is enhanced by the presence of Cu2+ or Zn2+. Our results provide a general strategy for the design of a series of hetero‐bimetallic catalysts for the reduction of CO2.

The Research work of Dr. Ishida ‐ including Syntheses and Their Photocatalytic CO2 Reduction of Dinuclear Metal Complexes with Peptide Linkages project

The process of photosynthesis holds potential to be harnessed for addressing increasing CO2 levels, as well as for finding solutions for energy shortages resulting from depleted fossil fuel reserves. Professor Hitoshi Ishida, Laboratory on Functional Metal Complexes, Kansai University, has extensive expertise in creating artificial enzymes and is interested in developing techniques to emulate photosynthesis. The plan is to create a new photocatalyst by combining photochemical CO2 reduction catalytic reactions for artificial photosynthesis with the technology of functional molecule design using ‘peptide origami’, whereby proteins fold to form higher-order structures and exhibit functions. Ishida and his team are seeking to achieve artificial photosynthesis by using ruthenium complexes as catalysts in CO2 reduction reactions that can reduce CO2 to carbon monoxide (CO) and formic acid (HCOOH), which are useful as energy sources. Ishida has created functional molecules combining metal complexes with proteins, including artificial metalloproteins ‐ a type of protein containing a metal ion ‐ using synthetic bipyridyl amino acid 5Bpy. This focused on a rare transition metal called ruthenium as the ruthenium complexes the researchers are investigating have a selectivity for carbon monoxide and formic acid reduction products that change depending on the reaction conditions. The ultimate goal of Ishida’s work is to find a solution to the problem of pollution, while addressing the need for alternatives to fossil fuels.

Reduction of CO2 in the presence of light via excited-state hydride transfer reaction in a NADPH-inspired derivative.

The photo-catalytic reduction of CO2 into chemical feedstocks using solar energy has attracted vast interest in environmental science because of global warming. Based on our previous study on the CO2 complex with one of the benzimidazoline (BI) derivatives, we explore the photochemical reduction of CO2 in one of the benzimidazoline derivatives (1,3-dimethyl-5,6-diol-2,3-dihydro-1H-benzimidazole) by quantum-chemical methods. Our results reveal that carbon dioxide can be reduced to formate (HCOO-) by a hydride transfer reaction in the excited state of this complex of benzimidazoline derivative and CO2. While the ground-state hydride transfer reaction in this complex exhibits a substantial barrier, a charge-transfer can occur in the first singlet excited state of the complex in the UV-A region (326 nm), and after overcoming a moderate barrier (∼0.4 eV) the system can have access to the products. The interaction with a polar solvent decreases further the barrier such that the reaction in dimethyl sulfoxide can proceed with a negligibly small barrier (∼0.1 eV) or in a nearly barrierless manner. Our results show that this benzimidazoline derivative may act as a catalyst in the photoreduction of CO2.

Electronic Effect Promoted Visible-Light-Driven CO2-to-CO Conversion in a Water-Containing System.

The design of unsaturated nonprecious metal complexes with high catalytic performance for photochemical CO2 reduction is still an important challenge. In this paper, four coordinatively unsaturated Co-salen complexes 1-4 were explored in situ using o-phenylenediamine derivatives and 5-methylsalicylaldehyde as precursors of the ligands in 1-4. It was found that complex 4, bearing a nitro substituent (-NO2) on the aromatic ring of the salen ligand, exhibits the highest photochemical performance for visible-light-driven CO2-to-CO conversion in a water-containing system, with TONCO and CO selectivity values of 5300 and 96%, respectively. DFT calculations and experimental results revealed that the promoted photocatalytic activity of 4 is ascribed to the electron-withdrawing effect of the nitro group in 4 compared to 1-3 (with -CH3, -F, and -H groups, respectively), resulting in a lower reduction potential of active metal centers CoII and lower barriers for CO2 coordination and C-O cleavage steps for 4 than those for catalysts 1-3.

Low-coordination transition metal sites on oxygen vacancy enriched strontium titanate-based perovskites enable highly selective photocatalytic CO2 reduction to CH4

The photochemical conversion of CO2 into high-value single hydrocarbon fuels such as CH4 remains a challenge. Here we have prepared a series of perovskites VO-SrTiMO3 (M = Mn, Fe, Co) with rich oxygen vacancies. Among them, Mn-doped perovskite (VO-STMn0.2) exhibited 18.21 μmol g−1 yield and nearly 100 % selectivity for CH4, as well as excellent reproducibility of about 15 h. Through a combination of advanced characterization and theoretical calculations, we found that the low-coordination transition metal site was able to stabilize the critical COOH* and CO* intermediates, thereby altering the reaction pathway to form CH4 instead of CO. Most importantly, this work demonstrated that the relative center between the 2p orbitals of the oxygen atom of the CO2 reduction intermediate and the 3d orbitals of the low-coordination metal site regulates the reaction mechanism of CO2 reduction, offering the possibility of achieving efficient photochemical reduction of CO2.

Porosity as a Design Element for Developing Catalytic Molecular Materials for Electrochemical and Photochemical Carbon Dioxide Reduction.

The catalytic reduction of carbon dioxide (CO2 ) using sustainable energy inputs is a promising strategy for upcycling of atmospheric carbon into value-added chemical products. This goal has inspired the development of catalysts for selective and efficient CO2 conversion using electrochemical and photochemical methods. Among the diverse array of catalyst systems designed for this purpose, two- and three-dimensional platforms that feature porosity offer the potential to combine carbon capture and conversion. Included are covalent organic frameworks (COFs), metal-organic frameworks (MOFs), porous molecular cages, and other hybrid molecular materials developed to increase active site exposure, stability, and water compatibility while maintaining precise molecular tunability. This mini-review showcases catalysts for the CO2 reduction reaction (CO2 RR) that incorporate well-defined molecular elements integrated into porous materials structures. Selected examples provide insights into how different approaches to this overall design strategy can augment their electrocatalytic and/or photocatalytic CO2 reduction activity. This article is protected by copyright. All rights reserved.

Unlocking full and fast conversion in photocatalytic carbon dioxide reduction for applications in radio-carbonylation

Harvesting sunlight to drive carbon dioxide (CO2) valorisation represents an ideal concept to support a sustainable and carbon-neutral economy. While the photochemical reduction of CO2 to carbon monoxide (CO) has emerged as a hot research topic, the full CO2-to-CO conversion remains an often-overlooked criterion that prevents a productive and direct valorisation of CO into high-value-added chemicals. Herein, we report a photocatalytic process that unlocks full and fast CO2-to-CO conversion (<10 min) and its straightforward valorisation into human health related field of radiochemistry with carbon isotopes. Guided by reaction-model-based kinetic simulations to rationalize reaction optimisations, this manifold opens new opportunities for the direct access to 11C- and 14C-labeled pharmaceuticals from their primary isotopic sources [11C]CO2 and [14C]CO2.

Recent Advances in Transition Metal Phosphide Nanocatalysts for H2 Evolution and CO2 Reduction

Green hydrogen energy has captivated researchers and is regarded as a feasible option for future energy-related aspirations. The emerging awareness of renewable energy-driven hydrogen generation and carbon dioxide reduction calls for the use of unconventional schematic tools in the fabrication of nanocatalyst systems. Transition metal phosphides are state-of-art, cost-effective, noble-metal-free materials that have been comprehensively examined for sustainable energy-driven applications. Recent reports on these advanced functional materials have cemented their candidature as high-performance catalytic systems for hydrogen production and for carbon dioxide conversion into value-added chemical feedstock. Bimetallic NiCoP (238.2 mmol g−1 h−1) exhibits top-notch catalytic competence toward photocatalytic HER that reveals the energy-driven application of a pristine class of TMPs, whereas heterostructured Ni2P/CdS was found to be fit for photochemical CO2 reduction, as well as for HER. On the other hand, pristine Ni2P was recently ascertained as an efficient electrocatalytic system for HER and CO2RR applications. A wide array of physicochemical modulations, such as compositional and structural engineering, defect generation, and facet control, have been used for improving the catalytic efficiency of transition metal phosphide nanostructures. In this review, we succinctly discuss the proficiency of transition metal phosphides in green hydrogen production and carbon dioxide conversion via photochemical and electrochemical pathways. We detail the significance of their structural properties and brief the readers about the synthetic advancements without deviating from our goal of summarizing the recent achievements in energy-driven applications.

Mixed Halide Formation in Lead‐Free Antimony‐Based Halide Perovskite for Boosted CO2 Photoreduction: Beyond Band Gap Tuning

AbstractPhotocatalytic conversion of carbon dioxide (CO2) into value‐added fuels is a vastly promising anthropogenic chemical carbon cycle to combat the greenhouse effect while meeting the ever‐increasing energy demand. Recently, lead‐based halide perovskites have demonstrated great potential in various applications including photochemical reduction of CO2. However, in view of lead toxicity, the exploration of a lead‐free alternative is crucial for long term application. Herein, a series of lead‐free mixed halide perovskites Cs3Sb2ClxBr9−x (0 ≤ x ≤ 9) is prepared via a facile antisolvent recrystallization technique, where the incorporation of a secondary halide enhances the charge transfer and separation while allowing precise tuning of bandgap between 2.59 and 2.90 eV. Theoretical calculations further reveal that the formation of mixed Cl/Br halides engenders favorable charge redistribution due to lower octahedral distortion, which in turn strengthens CO2 adsorption and activation. Under visible light illumination, the optimal dual halide perovskite, Cs3Sb2Cl4Br5 manifests substantial twofold and fourfold enhancements of CH4 yield over the single halide perovskite, Cs3Sb2Br9 and Cs3Sb2Cl9, respectively. In brief, this study provides a compelling demonstration of lead‐free mixed halide perovskites for photocatalytic CO2 reduction, and it is anticipated to drive further application of perovskite‐based photocatalysts toward a diverse range of artificial photoredox reactions.

Solar‐Driven CO2 Conversion via Optimized Photothermal Catalysis in a Lotus Pod Structure

AbstractPhotothermal CO2 reduction is one of the most promising routes to efficiently utilize solar energy for fuel production at high rates. However, this reaction is currently limited by underdeveloped catalysts with low photothermal conversion efficiency, insufficient exposure of active sites, low active material loading, and high material cost. Herein, we report a potassium‐modified carbon‐supported cobalt (K+−Co−C) catalyst mimicking the structure of a lotus pod that addresses these challenges. As a result of the designed lotus‐pod structure which features an efficient photothermal C substrate with hierarchical pores, an intimate Co/C interface with covalent bonding, and exposed Co catalytic sites with optimized CO binding strength, the K+−Co−C catalyst shows a record‐high photothermal CO2 hydrogenation rate of 758 mmol gcat−1 h−1 (2871 mmol gCo−1 h−1) with a 99.8 % selectivity for CO, three orders of magnitude higher than typical photochemical CO2 reduction reactions. We further demonstrate with this catalyst effective CO2 conversion under natural sunlight one hour before sunset during the winter season, putting forward an important step towards practical solar fuel production.