Light-driven CO2 Research Articles

Co Cluster-Modified Ni Nanoparticles with Superior Light-Driven Thermocatalytic CO2 Reduction by CH4

Excessive fossil burning causes energy shortages and contributes to the environmental crisis. Light-driven thermocatalytic CO2 reduction by methane (CRM) provides an effective strategy to conquer these two global challenges. Ni-based catalysts have been developed as candidates for CRM that are comparable to the noble metal catalysts. However, they are prone to deactivation due to the thermodynamically inevitable coking side reactions. Herein, we reported a novel Co-Ni/SiO2 nanocomposite of Co cluster-modified Ni nanoparticles, which greatly enhance the catalytic durability for light-driven thermocatalytic CRM. It exhibits high production rates of H2 (rH2) and CO (rCO, 22.8 and 26.7 mmol min−1 g−1, respectively), and very high light-to-fuel efficiency (ƞ) is achieved (26.8%). Co-Ni/SiO2 shows better catalytic durability than the referenced catalyst of Ni/SiO2. Based on the experimental results of TG-MS, TEM, and HRTEM, we revealed the origin of the significantly enhanced light-driven thermocatalytic activity and durability as well as the novel photoactivation. It was discovered that the focused irradiation markedly reduces the apparent activation energy of CO2 on the Co-Ni/SiO2 nanocomposite, thus significantly enhancing the light-driven thermocatalytic activity.

Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water

Molecular catalyst coordinatively bonded to organic semiconductors for selective light-driven CO2 reduction in water

Near-Infrared Light-Driven CO2 Reduction on Cup-Stacked Carbon Nanotubes.

Carbon nanotubes feature one-dimensional nature of collective excitations, wherein strong confinement of surface plasmons severely hinders the liberation of hot electrons (HEs), posing grand challenges for their utilization in photochemistry. In this study, we prototypically achieved directed HEs flow and extraction in hybrid plasmonic CNN based on cup-stacked carbon nanotubes (CSCNTs), taking advantage of their privileged edge-plane sites. The localized pz electronic states and accessible intersubband plasmon excitations in the near-infrared (NIR) regime stands in striking contrast to the conventional concentric carbon nanotubes, as evidenced by combined photo-induced force microscopy (PiFM) and transient photocurrent response. The hybrid comprising intimately integrated CSCNTs-C3N4 effectively sustains interfacial electronic states and underlies the energy extraction out of plasmonic components. The CNN demonstrates almost near-unity NIR light-driven CO2 reduction to CO with a rate of 1.35 µmol g-1 h-1. This work sheds light on the exploitation of metal-free carbon-based plasmonic nanostructures for photocatalytic applications.

Photocatalytic CO2 Reduction by Near-Infrared-Light (1200 nm) Irradiation and a Ruthenium-Intercalated NiAl-Layered Double Hydroxide.

Near-infrared light-driven photocatalytic CO2 reduction (NIR-CO2PR) holds tremendous promise for the production of valuable commodity chemicals and fuels. However, designing photocatalysts capable of reducing CO2 with low energy NIR photons remains challenging. Herein, a novel NIR-driven photocatalyst comprising an anionic Ru complex intercalated between NiAl-layered double hydroxide nanosheets (NiAl-Ru-LDH) is shown to deliver efficient CO2 photoreduction (0.887 μmol h-1) with CO selectivity of 84.81 % under 1200 nm illumination and excellent stability over 50 testing cycles. This remarkable performance results from the intercalated Ru complex lowering the LDH band gap (0.98 eV) via a compression-related charge redistribution phenomenon. Furthermore, transient absorption spectroscopy data verified light-induced electron transfer from the Ru complex towards the LDH sheets, increasing the availability of electrons to drive CO2PR. The presence of hydroxyl defects in the LDH sheets promotes the adsorption of CO2 molecules and lowers the energy barriers for NIR-CO2PR to CO. To our knowledge, this is one of the first reports of NIR-CO2PR at wavelengths up to 1200 nm in LDH-based photocatalyst systems.

Visible Light-Driven CO2 Capture and Release Using Photoactive Pyranine in Water in Continuous Flow.

The urgent need to address climate change and its environmental consequences demands innovative carbon capture technologies, given the relationship between rising global temperatures and increased atmospheric CO2 levels. Here, we present a reversible photochemical carbon capture and release strategy and system utilizing photoactive pyranine in an aqueous bicarbonate buffer system. Control experiments suggested that the photoacid effect occurs at the surface which contributes to CO2 release, complemented by the photothermal effect at the surface and in the bulk. A continuous flow setup employing a tube-in-tube configuration with a hollow fiber membrane demonstrates the efficiency and reliability of the visible light-driven carbon capture system, with the release of CO2 captured from a 15% CO2 feed in the dark, at a rate of 0.48 mmol CO2 per hour to a nitrogen sweep stream under light irradiation at 200 W/m2, a level comparable to solar intensity of visible light (150 W/m2 of blue light -250 W/m2 of blue and green light). The robustness and scalability of the system has been demonstrated, with long-term operation over 7 days yielding 60 mmol (1.34 L CO2 at STP) of cumulated CO2 separation. Additionally, we explored the potential for direct air capture, yielding 3 μmol of CO2 separation over 2 h of operation from a bicarbonate buffer solution saturated with ambient air (420 ppm). This work introduces the prospect of photoswing of carbon capture systems, which can avoid external energy input beyond solar irradiation, offering promising avenues for addressing the challenges associated with climate change.

Rationally Designed S-Scheme CeO2/g-C3N4 Heterojunction for Promoting Visible Light Driven CO2 Photoreduction into Syngas.

Exploring low-cost visible light photocatalysts for CO2 reduction to produce proportionally adjustable syngas is of great significance for meeting the needs of green chemical industry. A S-Scheme CeO2/g-C3N4 (CeO2/CN) heterojunction was constructed by using a simple two-step calcination method. During the photocatalytic CO2 reduction process, the CeO2/CN heterojunction can present a superior photocatalytic performance, and the obtained CO/H2 ratios in syngas can be regulated from 1 : 0.16 to 1 : 3.02. In addition, the CO and H2 production rate of the optimal CeO2/CN composite can reach 1169.56 and 429.12 μmol g-1 h-1, respectively. This superior photocatalytic performance is attributed to the unique S-Scheme photogenerated charge transfer mechanism between CeO2 and CN, which facilitates rapid charge separation and migration, while retaining the excellent redox capacity of both semiconductors. Particularly, the variable valence Ce3+/Ce4+ can act as electron mediator between CeO2 and CN, which can promote electron transfer and improve the catalytic performance. This work is expected to provide a new useful reference for the rational construction of high efficiency S-Scheme heterojunction photocatalyst, and improve the efficiency of photocatalytic reduction of CO2, promoting the photocatalytic reduction of CO2 into useful fuels.

Praseodymium orthovanadate-waste PET bottle derived sulfur doped carbon for efficient Z-scheme photocatalytic CO2 reduction

Escalating amounts of carbon dioxide (CO2) in the Earth's atmosphere are a major cause of climate change and its negative consequences, making it a global concern. The present work highlights the intersection of waste management, resource utilization, and climate change mitigation, showcasing the potential for an additional sustainable and circular economy. Synthesizing carbon from waste polyethylene terephthalate (PET) bottles is an eco-friendly approach. X-ray diffraction, Raman spectroscopic, scanning electron microscopic, tunnelling electron microscopic, infrared fourier transform spectroscopy (FTIR) and X-ray photoelectron spectroscopic results indicate the effective extraction of carbon doped with sulfur (S@C) and the successive formation of nanocomposite with PrVO4 (PrV/S@C). Superior photocatalytic activity was observed under visible light compared to UV light. PrV/S@C showed enhanced light-driven CO2 reduction compared to pristine materials and was found to evolve 39, 56, and 98 µmol h−1 g−1 of H2, CH4 and CO, respectively. The effect of reaction temperature was examined and optimized at 100 °C. The enhanced activity in PrV/S@C compared to PrV and S@C probably due to the increased surface area, conductivity and synergy. In-Situ Diffused reflectance (DRIFT-IR) and liquid chromatography mass spectroscopy (LC-MS) confirm the evolution of CO and CH4. The optical, photo/electrochemical, Scavenger studies, Electron spin resonance (ESR) and Mott-Schottky studies suggest the formation of a direct Z-scheme photoredox reaction in the presence of PrV/S@C and sacrificial gent. The reusability studies for 5 cycles indicate good stability with a slight deviation in structure and morphology of PrV/S@C, as observed in XRD and SEM. Tackling plastic pollution and generating value-added carbonaceous products through CO2 reduction is the twin application of the present work that has piqued the interest of several researchers in environmental remediation.

Light-driven CO2 utilization for chemical production in bacterium biohybrids

Artificial photosynthetic systems provide an alternative approach for the sustainable, efficient, and versatile production of biofuels and biochemicals. However, improving the efficiency of electron transfer between semiconductor materials and microbial cells remains a challenge. In this study, an inorganic-biological photosynthetic biohybrid system (IBPHS) consisting of photocatalytic and biocatalytic modules was developed by integrating cadmium telluride quantum dots (CdTe QDs) with Escherichia coli cells. A photocatalytic module was constructed by biosynthesizing CdTe QDs to capture light and generate electrons. The biocatalytic module was built by converting photo-induced electrons to enhance NADH regeneration; thus, the NADH content in E. coli under blue light increased by 5.1-fold compared to that in darkness. Finally, IBPHS was utilized to drive CO2 reduction pathways for versatile bioproduction such as formate and pyruvate, with CO2 utilization rates up to 51.98 and 21.92 mg/gDCW/h, respectively, exceeding that of cyanobacteria. This study offers a promising platform for the rational design of biohybrids for efficient biomanufacturing processes with high complexity and functionality.

Mononuclear Iron Pyridinethiolate Complex Promoted CO2 Photoreduction via Rapid Intramolecular Electron Transfer.

Designing earth-abundant metal complexes as efficient molecular photocatalysts for visible light-driven CO2 reduction is a key challenge in artificial photosynthesis. Here, we demonstrated the first example of a mononuclear iron pyridine-thiolate complex that functions both as a photosensitizer and catalyst for CO2 reduction. This single-component bifunctional molecular photocatalyst efficiently reduced CO2 to formate and CO with a total turnover number (TON) of 46 and turnover frequency (TOF) of 11.5 h-1 in 4 h under visible light irradiation. Notably, the quantum yield was determined to be 8.4 % for the generation of formate and CO at 400 nm. Quenching experiments indicate that high photocatalytic activity is mainly attributed to the rapid intramolecular quenching protocol. The mechanism investigation by DFT calculation and electrochemical studies revealed that the protonation of Febpy(pyS)2 is indispensable step for photocatalytic CO2 reduction.

Assisting Bi2Fe4O9 nanosheets with CeO2@PANACSs macro-spheres as bifunctional supporter for enhanced photocatalytic CO2 reduction

The efficient capture of CO2 molecules is a crucial step in the light-driven CO2 synthesis of high value-added products. In this work, CeO2 is embedded in polyacrylonitrile-based carbon spheres (PANACSs) via a suspension polymerization and carbonization method to synthesise CeO2@PANACSs with bifunction (CO2 adsorption and reduction ablity), and the strong oxidising capacity Bi2Fe4O9 was coupled to obtain ternary Bi2Fe4O9/CeO2@PANACSs composites with high adsorption-reduction capacity for CO2. The effective synergistic effects between Bi2Fe4O9 and CeO2@PANACSs realize that the CO yield of ternary hybrid photocatalyst can reach as high as 256.1 μmol g−1 for 10 h, approximately 19.55 times, 1.45 times and 1.62 times higher than that of pristine PANACSs, Bi2Fe4O9 and CeO2, respectively. The exceptional performance of Bi2Fe4O9/CeO2@PANACSs composites is mainly attributed to the synergistic effect of the ternary system, which not only provides CO2-rich adsorption-reduction active sites but also effectively inhibits photogenerated electron-hole complexation. Meanwhile, the outer layer of Bi2Fe4O9 with its excellent oxidising capacity also provides a large amount of H* to ensure efficient hydrodeoxygenation of CO2. Finally, combined with the results of in situ fourier transform infrared spectra, a possible mechanism for the photocatalytic reduction of CO2 over ternary photocatalysts is proposed. Our finding provides a noteworthy promising strategy to construct bifunctional composite photocatalysts for achieving the high-efficient CO2 adsorption and photoreduction to CO.

Synergetic effect for highly efficient light-driven CO2 reduction by CH4 on Co/Mg-CoAl2O4 promoted by a photoactivation

The utilization of photothermocatalytic dry reforming of methane is shown to be an up-and-coming technology. However, reaching high fuel productivity at a comparatively low light intensity and effectively suppressing the side reactions of coking in the DRM process are still two tough difficulties. Under focused UV–vis–IR irradiation at a relatively low light intensity of 80.5 kW m−2, a nanostructure of Co/Mg-CoAl2O4 possesses excellent photothermocatalytic activity and a light-to-fuel efficiency of 34.2 % and a low carbon deposition rate compared to its reference catalyst without Mg2+ doping (Co/CoAl2O4). The improved photothermocatalytic activity and coking resistance of Co/Mg-CoAl2O4 mainly comes from the synergetic effect, including Mg2+ doping, the active lattice oxygen in CoAl2O4 also participating in the oxidation of carbon species, and strong light absorption properties of the Mg-CoAl2O4. The photoactivation promotes DRM on Co nanoparticles while significantly facilitates the C* oxidation by strongly adsorbed CO2 on doped Mg2+.

The cooperative performance of iodo and copper in a Zr-based UiO-67 metal-organic framework for highly selective photocatalytic CO2 reduction to methanol

Photocatalytic CO2 reduction (PCR) to fuels using metal-organic frameworks (MOFs) offers promising solutions for both enhancing energy supply and mitigating global warming. However, research addressing the selectivity towards MeOH production, the role of CO2 uptake in productivity, and the identification of intermediates remains limited. Herein, we present an iodo/copper functionalization strategy for the Zr-based UiO-67 MOF. The resulting bifunctional Cu/I2-Zr-BPDC/BPyDC exhibited remarkable selectivity in light-driven CO2 reduction to MeOH, revealing the first investigation of halogen bonding's effect on PCR. Crucially, Cu/I2-Zr-BPDC/BPyDC surpassed not only pristine Zr-BPyDC, I2-Zr-BPDC, and Cu-Zr-BPyDC, but also boasted the best catalytic performance among reported MOFs. Furthermore, Cu/I2-Zr-BPDC/BPyDC demonstrated a CO2 uptake capacity of 48.6 mg g−1, 1.7 times greater than non-modified Zr-BPyDC, suggesting a direct correlation between CO2 adsorption efficiency and CO2 conversion. In addition to assigning CuII ↔ CuI catalytic cycle, collaborative performance of I and Cu functions in CO2 activation was traced by infrared spectra that elucidate the CI…OCO interaction and Cu…CO2/CuCO2H complex formation. This work provides valuable insights for engineering selective and high-performance PCR catalyst through the rational incorporation of functionalities within MOFs.

Visible light-driven CO2 photoreduction by a Re(I) complex immobilized onto CuO/Nb2O5 heterojunctions.

The immobilization of Re(I) complexes onto metal oxide surfaces presents an elegant strategy to enhance their stability and reusability toward photocatalytic CO2 reduction. In this study, the photocatalytic performance of fac-[ClRe(CO)3(dcbH2)], where dcbH2 = 4,4'-dicarboxylic acid-2,2'-bipyridine, anchored onto the surface of 1%m/m CuO/Nb2O5 was investigated. Following adsorption, the turnover number for CO production (TONCO) in DMF/TEOA increased significantly, from ten in solution to 370 under visible light irradiation, surpassing the TONCO observed for the complex onto pristine Nb2O5 or CuO surfaces. The CuO/Nb2O5 heterostructure allows for efficient electron injection by the Re(I) center, promoting efficient charge separation. At same time CuO clusters introduce a new absorption band above 550nm that contributes for the photoreduction of the reaction intermediates, leading to a more efficient CO evolution and minimization of side reactions.

Synthesis and characterization of cobalt-based layered double hydroxides for light-driven CO2 reduction

The influence of cobalt on the photocatalytic reduction of CO2 under visible light was examined by using various 3:1 Co-Mg/Al layered double hydroxides (LDHs) obtained by coprecipitation under low oversaturation conditions. CO2 photoreduction increased with increasing amount of cobalt in the solids. Calcining the LDHs gave basic mixed oxides (LDOs) with considerably decreased activity, thus confirming that the hydroxyl structure of the materials facilitated the photocatalytic process. Attempts at reconstructing the LDOs revealed that only the material with the smallest amount of cobalt regained its original structure —and exhibited excellent performance in the reaction. All solids were characterized by using various instrumental techniques and used as catalysts in the photocatalytic reduction of CO2. Also, the fully reconstructed material was reused with no substantial loss of activity.

Fabrication and optimization of perovskite-based photoanodes for solar-driven CO2 photoelectroreduction to formate

The photoelectrochemical reduction of CO2 to value-added products represents a promising strategy for mitigating CO2 emissions. However, further research efforts need to be undertaken to enable the technology for scale-up, including the design and fabrication of efficient photoelectrodes capable of yielding substantial photogenerated current densities. In this work, a photoanode combining a commercial calcium titanate perovskite (CaTiO3) and BiVO4 layers coated onto a transparent FTO substrate by automated spray pyrolysis is proposed. Different photoanode configurations are tested, with the most favourable results achieved when BiVO4 is positioned as the top layer with back illumination. The optimization of the catalytic loading is also assessed, finding an optimal at 1 mg cm−2 of CaTiO3 and 3 mg cm−2 of BiVO4, resulting in an impressive current density of –71 mA cm−2 at –1.8 V vs. Ag/AgCl. This optimal photoanode is then integrated into an electrolyzer for continuous visible light-driven CO2 reduction in the gas phase to formate, obtaining a concentration of 63.8 g L−1, with a Faradaic Efficiency of 79.1 %, and solar-to-fuel conversion efficiency of 7.6 %. These results represent a significant advancement in the development of photoanodes, offering promise for the future scalability of photoelectrochemical CO2 reduction processes.

Visible-light-responsive hybrid photocatalysts for quantitative conversion of CO2 to highly concentrated formate solutions.

Photocatalysts can use visible light to convert CO2 into useful products. However, to date photocatalysts for CO2 conversion are limited by insufficient long-term stability and low CO2 conversion rates. Here we report hybrid photocatalysts consisting of conjugated polymers and a ruthenium(ii)-ruthenium(ii) supramolecular photocatalyst which overcome these challenges. The use of conjugated polymers allows for easy fine-tuning of structural and optoelectronic properties through the choice of monomers, and after loading with silver nanoparticles and the ruthenium-based binuclear metal complex, the resulting hybrid systems displayed remarkably enhanced activity for visible light-driven CO2 conversion to formate. In particular, the hybrid photocatalyst system based on poly(dibenzo[b,d]thiophene sulfone) drove the very active, durable and selective photocatalytic CO2 conversion to formate under visible light irradiation. The turnover number was found to be very high (TON = 349 000) with a similarly high turnover frequency (TOF) of 6.5 s-1, exceeding the CO2 fixation activity of ribulose-1,5-bisphosphate carboxylase/oxygenase in natural photosynthesis (TOF = 3.3 s-1), and an apparent quantum yield of 11.2% at 440 nm. Remarkably, quantitative conversion of CO2 (737 μmol, 16.5 mL) to formate was achieved using only 8 mg of the hybrid photocatalyst containing 80 nmol of the supramolecular photocatalyst at standard temperature and pressure. The system sustained photocatalytic activity even after further replenishment of CO2, yielding a very high concentration of formate in the reaction solution up to 0.40 M without significant photocatalyst degradation within the timeframe studied. A range of experiments together with density functional theory calculations allowed us to understand the activity in more detail.

Localized surface plasmon resonance effect of bismuth nanoparticles in Bi/TiO2 catalysts for boosting visible light-driven CO2 reduction to CH4

Herein, the photocatalysts of metallic Bi-modified TiO2 microsphere (namely BTO) were synthesized by one-pot solvothermal method. The localized surface plasmon resonance (LSPR) effect of introduced metallic Bi nanoparticles is beneficial to improve the absorption efficiency for visible light, and its surface hot electrons can donate to the valence band of TiO2 for boosting the separation efficiency of light generated electron-hole pairs. BTO catalysts exhibit the super catalytic activity for visible light-driven CO2 reduction with H2O to CH4. The formation amount and selectivity of CH4 product over BTO-2 catalyst are 49.12 μmol g−1 and 85.48 % for 4 h, respectively. Based on the results of in-situ DRIFTS and density functional theory calculation, the mechanism for photocatalytic CO2 reduction is proposed: the visible light-driven LSPR effect on BTO catalyst can boost the key step of CO2* -to-HCO* for promoting selective generation of CH4 product. It inspires the design of efficient photocatalysts for CO2 conversion.

Boosting photocatalytic CO2 reduction efficiency by graphene nanoflakes (GNF) decorated ZIF-67 under visible light irradiation

The design and development of sustainable and cost-effective photocatalysts necessitate significant effort for improved CO2 reduction efficiency. Metal-organic frameworks (MOFs), with high surface area, are gaining popularity in photocatalysis, but their high electron-hole (e-, h+) recombination and low light harvesting capacity limit their utility. Graphene nanoflake (GNF) is a novel, low-cost carbon nanomaterial which has received attention owing to its non-toxicity, high aqueous solubility, unique photoluminescence properties, and excellent photostability. In this work, graphene nanoflake (GNF) decorated zeolitic imidazole framework ZIF-67 (GNF(X)/ZIF-67) has been synthesized for improving visible light-driven photocatalytic CO2 reduction performance. The composite GNF6/ZIF-67 decorated with 6% GNF nanoflake achieves the highest methanol generation of 50.93 µmolg−1 and the highest ethanol generation of 33.97 µmolg−1 after 8 h of visible light irradiation, compared to pure ZIF-67 which is 1.93 and 1.59 times respectively. The effect of GNF on boosting the visible-light photocatalytic activity of ZIF-67 was explored based on the UV-Vis DRS spectra, electrochemical impedance spectra (EIS), transient photocurrent response, and photoluminescence (PL) experiment. This work may discover a new way to synthesize photocatalysts for applying CO2 photoreduction.

Light-driven thermocatalytic CO2 reduction by CH4 on alumina-cluster-modified Ni nanoparticles with excellent durability and high light-to-fuel efficiency promoted by the photoactivation effect

Using inexhaustible solar energy to drive efficient light-driven thermocatalytic CO2 reduction by CH4 (DRM) is an attractive approach that can synchronously reduce the greenhouse effect and convert solar energy into fuels. However, it is often limited by the intense light intensity required to produce high fuel production rates, and the catalyst deactivation due to severe carbon deposition generated from side reactions. Herein, a nanostructure of alumina-cluster-modified Ni nanoparticles supported on Al2O3 nanorods (ACM-Ni/Al2O3) was synthesized, displaying good catalytic performance under focused UV–vis-IR illumination. By light-driven thermocatalytic DRM on ACM-Ni/Al2O3 at a reduced light intensity of 76.9 kW m−2, the high fuel production rates of H2 (rH2, 65.7 mmol g−1 min−1) and CO (rCO, 78.8 mmol g−1 min−1), as well as an efficient light-to-fuel efficiency (η, 26.3 %) are achieved without additional heating. The rH2 and rCO of light-driven thermocatalysis are 2.9 and 1.9 times higher, respectively, compared to conventional thermocatalysis at the same temperature. We have discovered that high light-driven thermocatalytic activity originates from the photoactivation effect, significantly reducing the apparent activation energy and facilitating C* oxidation as a decisive step in DRM. ACM-Ni/Al2O3 possesses excellent durability and exhibits an extremely low coking rate of 4.40 × 10−3 gc gcatalyst−1 h−1, which is 26.8 times lower than that of the reference sample without Al2O3 cluster modification (R-Ni/Al2O3). This is owing to a decrease in activation energies (Ea) of C* oxidation and an increase in Ea of C* polymerization by the surface modification of Ni nanoparticles with Al2O3 clusters, effectively inhibiting carbon deposition.

Light-Driven CO2 Reduction with a Surface-Displayed Enzyme Cascade-C3N4 Hybrid.

Efficient and cost-effective conversion of CO2 to biomass holds the potential to address the climate crisis. Light-driven CO2 conversion can be realized by combining inorganic semiconductors with enzymes or cells. However, designing enzyme cascades for converting CO2 to multicarbon compounds is challenging, and inorganic semiconductors often possess cytotoxicity. Therefore, there is a critical need for a straightforward semiconductor biohybrid system for CO2 conversion. Here, we used a visible-light-responsive and biocompatible C3N4 porous nanosheet, decorated with formate dehydrogenase, formaldehyde dehydrogenase, and alcohol dehydrogenase to establish an enzyme-photocoupled catalytic system, which showed a remarkable CO2-to-methanol conversion efficiency with an apparent quantum efficiency of 2.48% in the absence of externally added electron mediator. To further enable the in situ transformation of methanol into biomass, the enzymes were displayed on the surface of Komagataella phaffii, which was further coupled with C3N4 to create an organic semiconductor-enzyme-cell hybrid system. Methanol was produced through enzyme-photocoupled CO2 reduction, achieving a rate of 4.07 mg/(L·h), comparable with reported rates from photocatalytic systems employing mediators or photoelectrochemical cells. The produced methanol can subsequently be transported into the cell and converted into biomass. This work presents a sustainable, environmentally friendly, and cost-effective enzyme-photocoupled biocatalytic system for efficient solar-driven conversion of CO2 within a microbial cell.