A synergetic cocatalyst for conversion of carbon dioxide, sunlight, and water into methanol.

The conversion of CO2 into liquid fuels, using only sunlight and water, offers a promising path to carbon neutrality. An outstanding challenge is to achieve high efficiency and product selectivity. Here, we introduce a wireless photocatalytic architecture for conversion of CO2 and water into methanol and oxygen. The catalytic material consists of semiconducting nanowires decorated with core-shell nanoparticles, with a copper-rhodium core and a chromium oxide shell. The Rh/CrOOH interface provides a unidirectional channel for proton reduction, enabling hydrogen spillover at the core-shell interface. The vectorial transfer of protons, electrons, and hydrogen atoms allows for switching the mechanism of CO2 reduction from a proton-coupled electron transfer pathway in aqueous solution to hydrogenation of CO2 with a solar-to-methanol efficiency of 0.22%. The reported findings demonstrate a highly efficient, stable, and scalable wireless system for synthesis of methanol from CO2 that could provide a viable path toward carbon neutrality and environmental sustainability.

Unveiling the role of proton concentration in dinuclear metal complexes for boosting photocatalytic CO2 reduction.

The reaction kinetics of photocatalytic CO2 reduction is highly dependent on the transfer rate of electrons and protons to the CO2 molecules adsorbed on catalytic centers. Studies on uncovering the proton effect in catalysts on photocatalytic activity of CO2 reduction are significant but rarely reported. In this paper, we, from the molecular level, revealed that the photocatalytic activity of CO2 reduction is closely related to the proton availability in catalysts. Specifically, four dinuclear Co(II) complexes based on Robson-type ligands with different number of carboxylic groups (-nCOOH; n = 0, 2, 4, 6) were designed and synthesized. All these complexes show photocatalytic activity for CO2 reduction to CO in a water-containing system upon visible-light illumination. Interestingly, the CO yields increase positively with the increase of the carboxylic-group number in dinuclear Co(II) complexes. The one containing -6COOH shows the best photocatalytic activity for CO2 reduction to CO, with the TON value reaching as high as 10,294. The value is 1.8, 3.4, and 7.8 times higher than those containing -4COOH, -2COOH, and -0COOH, respectively. The high TON value also makes the dinuclear Co(II) complex with -6COOH outstanding among reported homogeneous molecular catalysts for photocatalytic CO2 reduction. Control experiments and density functional theory calculation indicated that more carboxylic groups in the catalyst endow the catalyst with more proton relays, thus accelerating the proton transfer and boosting the photocatalytic CO2 reduction. This study, at a molecular level, elucidates that more carboxylic groups in catalysts are beneficial for boosting the reaction kinetics of photocatalytic CO2 reduction.

Boosting CO2 photoreduction by π-π-induced preassembly between a Cu(I) sensitizer and a pyrene-appended Co(II) catalyst.

The design of a highly efficient system for CO2 photoreduction fully based on earth-abundant elements presents a challenge, which may be overcome by installing suitable interactions between photosensitizer and catalyst to expedite the intermolecular electron transfer. Herein, we have designed a pyrene-decorated Cu(I) complex with a rare dual emission behavior, aiming at additional π-interaction with a pyrene-appended Co(II) catalyst for visible light-driven CO2-to-CO conversion. The results of 1H NMR titration, time-resolved fluorescence/absorption spectroscopies, quantum chemical simulations, and photocatalytic experiments clearly demonstrate that the dynamic π-π interaction between sensitizer and catalyst is highly advantageous in photocatalysis by accelerating the intermolecular electron transfer rate up to 6.9 × 105 s-1, thus achieving a notable apparent quantum yield of 19% at 425 nm with near-unity selectivity. While comparable to most earth-abundant molecular systems, this value is over three times of the pyrene-free system (6.0%) and far surpassing the benchmarking Ru(II) tris(bipyridine) (0.3%) and Ir(III) tris(2-phenylpyridine) (1.4%) photosensitizers under parallel conditions.

Boosted C-C coupling with Cu-Ag alloy sub-nanoclusters for CO2-to-C2H4 photosynthesis.

The selective photocatalytic conversion of CO2 and H2O to high value-added C2H4 remains a great challenge, mainly attributed to the difficulties in C-C coupling of reaction intermediates and desorption of C2H4* intermediates from the catalyst surface. These two key issues can be simultaneously overcome by alloying Ag with Cu which gives enhanced activity to both reactions. Herein, we developed a facile stepwise photodeposition strategy to load Cu-Ag alloy sub-nanoclusters (ASNCs) on TiO2 for CO2 photoreduction to produce C2H4. The optimized catalyst exhibits a record-high C2H4 formation rate (1110.6 ± 82.5 µmol g-1 h-1) with selectivity of 49.1 ± 1.9%, which is an order-of-magnitude enhancement relative to current work for C2H4 photosynthesis. The in situ FT-IR spectra combined with DFT calculations reveal the synergistic effect of Cu and Ag in Cu-Ag ASNCs, which enable an excellent C-C coupling capability like Ag and promoted C2H4* desorption property like Cu, thus advancing the selective and efficient production of C2H4. The present work provides a deeper understanding on cluster chemistry and C-C coupling mechanism for CO2 reduction on ASNCs and develops a feasible strategy for photoreduction CO2 to C2 fuels or industrial feedstocks.

Molecular oxidation-reduction junctions for artificial photosynthetic overall reaction.

Constructing redox semiconductor heterojunction photocatalysts is the most effective and important means to complete the artificial photosynthetic overall reaction (i.e., coupling CO2 photoreduction and water photo-oxidation reactions). However, multiphase hybridization essence and inhomogeneous junction distribution in these catalysts extremely limit the diverse design and regulation of the modes of photogenerated charge separation and transfer pathways, which are crucial factors to improve photocatalytic performance. Here, we develop molecular oxidation-reduction (OR) junctions assembled with oxidative cluster (PMo12, for water oxidation) and reductive cluster (Ni5, for CO2 reduction) in a direct (d-OR), alternant (a-OR), or symmetric (s-OR) manner, respectively, for artificial photosynthesis. Significantly, the transfer direction and path of photogenerated charges between traditional junctions are obviously reformed and enriched in these well-defined crystalline catalysts with monophase periodic distribution and thus improve the separation efficiency of the electrons and holes. In particular, the charge migration in s-OR shows a periodically and continuously opposite mode. It can inhibit the photogenerated charge recombination more effectively and enhance the photocatalytic performance largely when compared with the traditional heterojunction models. Structural analysis and density functional theory calculations disclose that, through adjusting the spatial arrangement of oxidation and reduction clusters, the energy level and population of the orbitals of these OR junctions can be regulated synchronously to further optimize photocatalytic performance. The establishment of molecular OR junctions is a pioneering important discovery for extremely improving the utilization efficiency of photogenerated charges in the artificial photosynthesis overall reaction.

Ordered heterogeneity of molecular photosensitizer toward enhanced photocatalysis.

SignificanceThe photosensitizer is one of the important components in the photocatalytic system. Molecular photosensitizers have well-defined structures, which is beneficial in revealing the catalysis mechanism and helpful for further structural design and performance optimization. However, separation and recycling of the molecular photosensitizers is a great problem. Loading them into/on two/three-dimensional supports through covalent bonds, electrostatic interactions, and supramolecular interactions is a method that enhances their separation and recycling capability. Nonetheless, the structures of the resulting composites are unclear. Thus, the development of highly crystalline heterogeneity methods for molecular photosensitizers, albeit greatly challenging, is meaningful and desirable in photocatalysis, through which heterogeneous photosensitizers with well-defined structures, definite catalysis mechanisms, and good catalytic performance would be expected.

Dual electronic effects achieving a high-performance Ni(II) pincer catalyst for CO2 photoreduction in a noble-metal-free system.

A carbazolide-bis(NHC) NiII catalyst (1; NHC, N-heterocyclic carbene) for selective CO2 photoreduction was designed herein by a one-stone-two-birds strategy. The extended π-conjugation and the strong σ/π electron-donation characteristics (two birds) of the carbazolide fragment (one stone) lead to significantly enhanced activity for photoreduction of CO2 to CO. The turnover number (TON) and turnover frequency (TOF) of 1 were ninefold and eightfold higher than those of the reported pyridinol-bis(NHC) NiII complex at the same catalyst concentration using an identical Ir photosensitizer, respectively, with a selectivity of ∼100%. More importantly, an organic dye was applied to displace the Ir photosensitizer to develop a noble-metal-free photocatalytic system, which maintained excellent performance and obtained an outstanding quantum yield of 11.2%. Detailed investigations combining experimental and computational studies revealed the catalytic mechanism, which highlights the potential of the one-stone-two-birds effect.

Tunable green syngas generation from CO2 and H2O with sunlight as the only energy input.

The carbon-neutral synthesis of syngas from CO2 and H2O powered by solar energy holds grand promise for solving critical issues such as global warming and the energy crisis. Here we report photochemical reduction of CO2 with H2O into syngas using core/shell Au@Cr2O3 dual cocatalyst-decorated multistacked InGaN/GaN nanowires (NWs) with sunlight as the only energy input. First-principle density functional theory calculations revealed that Au and Cr2O3 are synergetic in deforming the linear CO2 molecule to a bent state with an O-C-O angle of 116.5°, thus significantly reducing the energy barrier of CO2RR compared with that over a single component of Au or Cr2O3. Hydrogen evolution reaction was promoted by the same cocatalyst simultaneously. By combining the cooperative catalytic properties of Au@Cr2O3 with the distinguished optoelectronic virtues of the multistacked InGaN NW semiconductor, the developed photocatalyst demonstrated high syngas activity of 1.08 mol/gcat/h with widely tunable H2/CO ratios between 1.6 and 9.2 under concentrated solar light illumination. Nearly stoichiometric oxygen was evolved from water splitting at a rate of 0.57 mol/gcat/h, and isotopic testing confirmed that syngas originated from CO2RR. The solar-to-syngas energy efficiency approached 0.89% during overall CO2 reduction coupled with water splitting. The work paves a way for carbon-neutral synthesis of syngas with the sole inputs of CO2, H2O, and solar light.

Construction of an Electron Capture and Transfer Center for Highly Efficient and Selective Solar-Light-Driven CO2 Conversion.

Exploring high-efficiency photocatalysts for selective CO2 reduction is still challenging because of the limited charge separation and surface reactions. In this study, a noble-metal-free metallic VSe2 nanosheet was incorporated on g-C3N4 to serve as an electron capture and transfer center, activating surface active sites for highly efficient and selective CO2 photoreduction. Quasi in situ X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and femtosecond transient absorption spectroscopy (fs-TAS) unveiled that VSe2 could capture electrons, which are further transferred to the surface for activating active sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations revealed a kinetically feasible process for the formation of a key intermediate and confirmed the favorable production of CO on the VSe2/PCN (protonated C3N4) photocatalyst. As an outcome, the optimized VSe2/PCN composite achieved 97% selectivity for solar-light-driven CO2 conversion to CO with a high rate of 16.3 µmol·g-1·h-1, without any sacrificial reagent or photosensitizer. This work offers new insights into the photocatalyst design toward highly efficient and selective CO2 conversion.

Advances in Defect Engineering of Metal Oxides for Photocatalytic CO2 Reduction.

Photocatalytic CO2 reduction technology, capable of converting low-density solar energy into high-density chemical energy, stands as a promising approach to alleviate the energy crisis and achieve carbon neutrality. Semiconductor metal oxides, characterized by their abundant reserves, good stability, and easily tunable structures, have found extensive applications in the field of photocatalysis. However, the wide bandgap inherent in metal oxides contributes to their poor efficiency in photocatalytic CO2 reduction. Defect engineering presents an effective strategy to address these challenges. This paper reviews the research progress in defect engineering to enhance the photocatalytic CO2 reduction performance of metal oxides, summarizing defect classifications, preparation methods, and characterization techniques. The focus is on defect engineering, represented by vacancies and doping, for improving the performance of metal oxide photocatalysts. This includes advancements in expanding the photoresponse range, enhancing photogenerated charge separation, and promoting CO2 molecule activation. Finally, the paper provides a summary of the current issues and challenges faced by defect engineering, along with a prospective outlook on the future development of photocatalytic CO2 reduction technology.

One-Step Fabricated Sn0 Particle on S-Vacancies SnS2 to Accelerate Photoelectron Transfer for Sterling Photocatalytic CO2 Reduction in Pure Water Vapor Environment.

Promoting the proton-coupled electron transfer process in order to solve the sluggish carrier migration dynamics is an efficient way to accelerate the photocatalytic CO2 reduction (PCR) process. Herein, through the reduction of Sn4+ by amino and sulfhydryl groups, Sn0 particles are lodged in S-vacancies SnS2 nanosheets. The high conductance of Sn0 particles expedites the collection and transport of photogenerated electrons, activating the surrounding surface of unsaturated sulfur (Sx 2- ) and thus lowering the energy barrier for generation of *COOH. Meanwhile, S-vacancies boost H2 O adsorption while Sx 2- increases CO2 adsorption, as demonstrated by density functional theory (DFT), obtaining a selectivity of 97.88% CO and yield of 295.06 µmol g-1 h-1 without the addition of co-catalysts and sacrificial agents. This work provides a new approach to building a fast electron transfer interface between metal particles and semiconductors, which works in tandem with S-vacancies and Sx 2- to boost the efficiency of photocatalytic CO2 reduction to CO in pure water vapor environment.

Accelerating Charge Kinetics in Photocatalytic CO2 Reduction by Modulating the Cobalt Coordination in Heterostructures of Cadmium Sulfide/Metal-Organic Layer.

Artificial photocatalytic CO2 reduction (CO2R) holds great promise to directly store solar energy into chemical bonds. The slow charge and mass transfer kinetics at the triphasic solid-liquid-gas interface calls for the rational design of heterogeneous photocatalysts concertedly boosting interfacial charge transfer, local CO2 concentration, and exposure of active sites. To meet these requirements, in this study heterostructures of CdS/MOL (MOL = metal-organic layer) furnishing different redox Co sites are fabricated for CO2R photocatalysts. It is found that the coordination environment of Co is key to photocatalytic activity. The best catalyst ensemble comprising ligand-chelated Co2+ with the bipyridine electron mediator demonstrates a high CO yield rate of 1523 µmol h-1 gcat -1, selectivity of 95.8% and TON of 1462.4, which are ranked among the best seen in literature. Comprehensive photochemical and electroanalytical characterizations attribute the high CO2R performance to the improved photocarrier separation and charge kinetics originated from the proper energy band alignment and coordination chemistry. This work highlights the construction of 2D heterostructures and modulation of transition metal coordination to expedite the charge kinetics in photocatalytic CO2 reduction.

Atomically Contacted Cs3Bi2Br9 QDs@UiO-66 Composite for Photocatalytic CO2 Reduction.

Metal halide perovskite quantum dots (QDs) are widely studied in the field of photocatalytic CO2 due to their strong light absorption and long carrier migration length. However, it can not exhibit high catalytic performance because of the radiative recombination and the lack of effective catalytic sites. Metal organic frameworks (MOFs) encapsulated QDs can not only solve the aforementioned problems, but also maintain their own unique characteristics with ultra-high specific surfaces area and abundant metal sites. In this work, lead-free bismuth-based halide perovskite QDs are encapsulated into Zr-based MOF (UiO-66), which combines the advantages with high power conversion efficiency of QDs and the high surface area and porosity of UiO-66. In addition, benefiting from the close contact between the Cs3Bi2Br9 QDs and the UiO-66 enables the photogenerated electrons in the QDs to be rapidly transferred to the MOF. As a result, the Cs3Bi2Br9@UiO-66 composite exhibits a higher yield for photocatalytic CO2 reduction than that of the prepared large-sized composite of Cs3Bi2Br9 and UiO-66.

Exploring a Ni-N4 Active Site-Based Conjugated Microporous Polymer Z-Scheme Heterojunction Through Covalent Bonding for Visible Light-Driven Photocatalytic CO2 Conversion in Pure Water.

Designing photocatalysts with efficient charge transport and abundant active sites for photocatalytic CO2 reduction in pure water is considered a potential approach. Herein, a nickel-phthalocyanine containing Ni-N4 active sites-based conjugated microporous polymer (NiPc-CMP), offering highly dispersed metal active sites, satisfactory CO2 adsorption capability, and excellent light harvesting properties, is engineered as a photocatalyst. By virtue of the covalently bonded bridge, an atomic-scale interface between the NiPc-CMP/Bi2 WO6 Z-scheme heterojunction with strong chemical interactions is obtained. The interface creates directional charge transport highways and retains a high redox potential, thereby enhancing the photoexcited charge carrier separation and photocatalytic efficiency. Consequently, the optimal NiPc-CMP/Bi2 WO6 (NCB-3) achieves efficient photocatalytic CO2 reduction performance in pure water under visible-light irradiation without any sacrificial agent or photosensitizer, affording a CO generation rate of 325.9 µmol g-1 with CO selectivity of 93% in 8 h, outperforming those of Bi2 WO6 and NiPc-CMP, individually. Experimental and theoretical calculations reveal the promotion of interfacial photoinduced electron separation and the role of Ni-N4 active sites in photocatalytic reactions. This study presents a high-performance CMP-based Z-scheme heterojunction with an effective interfacial charge-transfer route and rich metal active sites for photocatalytic CO2 conversion.

General and Scalable Synthesis of Mesoporous 2D MZrO2 (M = Co, Mn, Ni, Cu, Fe) Nanocatalysts by Amorphous-to-Crystalline Transformation.

In modern heterogeneous catalysis, it remains highly challenging to create stable, low-cost, mesoporous 2D photo-/electro-catalysts that carry atomically dispersed active sites. In this work, a general shape-preserving amorphous-to-crystalline transformation (ACT) strategy is developed to dope various transition metal (TM) heteroatoms in ZrO2, which enabled the scalable synthesis of TMs/oxide with a mesoporous 2D structure and rich defects. During the ACT process, the amorphous MZrO2 nanoparticles (M = Fe, Ni, Cu, Co, Mn) are deposited within a confined space created by the NaCl template, and they transform to crystalline 2D ACT-MZrO2 nanosheets in a shape-preserving manner. The interconnected crystalline ACT-MZrO2 nanoparticles thus inherit the same structure as the original MZrO2 precursor. Owing to its rich active sites on the surface and abundant oxygen vacancies (OVs), ACT-CoZrO2 gives superior performance in catalyzing the CO2-to-syngas conversion as demonstrated by experiments and theoretical calculations. The ACT chemistry opens a general route for the scalable synthesis of advanced catalysts with precise microstructure by reconciliating the control of crystalline morphologies and the dispersion of heteroatoms.

Emerging ZnO Semiconductors for Photocatalytic CO2 Reduction to Methanol.

Carbon recycling is poised to emerge as a prominent trend for mitigating severe climate change and meeting the rising demand for energy. Converting carbon dioxide (CO2) into green energy and valuable feedstocks through photocatalytic CO2 reduction (PCCR) offers a promising solution to global warming and energy needs. Among all semiconductors, zinc oxide (ZnO) has garnered considerable interest due to its ecofriendly nature, biocompatibility, abundance, exceptional semiconducting and optical properties, cost-effectiveness, easy synthesis, and durability. This review thoroughly discusses recent advances in mechanistic insights, fundamental principles, experimental parameters, and modulation of ZnO catalysts for direct PCCR to C1 products (methanol). Various ZnO modification techniques are explored, including atomic size regulation, synthesis strategies, morphology manipulation, doping with cocatalysts, defect engineering, incorporation of plasmonic metals, and single atom modulation to boost its photocatalytic performance. Additionally, the review highlights the importance of photoreactor design, reactor types, geometries, operating modes, and phases. Future research endeavors should prioritize the development of cost-effective catalyst immobilization methods for solid-liquid separation and catalyst recycling, while emphasizing the use of abundant and non-toxic materials to ensure environmental sustainability and economic viability. Finally, the review outlines key challenges and proposes novel directions for further enhancing ZnO-based photocatalytic CO2 conversion processes.

Polyarene Oxides with Tunable Quinone Units for Photocatalytic CO2 Reduction: A Simple Strategy toward Effective and Selective Catalysts.

The photocatalytic transformation of carbon dioxide (CO2) into valuable chemicals is a challenging process that requires effective and selective catalysts. However, most polymer-based photocatalysts with electron donor-acceptor (D-A) structures are synthesized with a fixed D-A ratio by using expensive monomers. Herein, we report a simple strategy to prepare polyarene oxides (PAOs) with quinone structural units via oxidation treatment of polyarene (PA). The resultant PAOs show tunable D-A structures and electronic band positions depending on the degree of oxidation, which can catalyze the photoreduction of CO2 with water under visible light irradiation, generating CO as the sole carbonaceous product without H2 generation. Especially, the PAO with an oxygen content of 17.6% afforded the highest CO production rate of 161.9 µmol g-1 h-1. It is verified that the redox transformation between quinone and phenolic hydroxyl in PAOs achieves CO2 photoreduction coupled with water oxidation. This study provides a facile way to access conjugated polymers with a tunable D-A structure and demonstrates that the resultant PAOs are promising photocatalysts for CO2 reduction.

Core-shell engineered g-C3N4@ NaNbO3for enhancing photocatalytic reduction of CO2.

Photocatalytic reduction of carbon dioxide is a technology that effectively utilizes CO2and solar energy. Sodium niobate (NaNbO3) has received much attention in the field of photocatalysis due to its excellent photocatalytic properties. However, the application of NaNbO3in the field of photocatalysis is still limited by poor reaction to visible light and easy recombination of photo-generated carriers. Heterojunction with g-C3N4to construct core-shell structure can effectively improve the above problems. Combining the two can design a core-shell composite material that is beneficial for photocatalytic reduction of CO2. Herein, we prepared a core-shell heterojunction g-C3N4/NaNbO3by uniformly impregnating urea on the surface of NaNbO3chromium nanofibers with NaNbO3nanofibers prepared by electrospinning as a catalyst carrier, and urea as a precursor of g-C3N4. The core-shell structure of g-C3N4/NaNbO3was verified by a series of characterization methods such as XPS, XRD, and TEM. It was found that under the same conditions, the methanol yield of core-shell g-C3N4/NaNbO3was 12.86µmol·g-1·h-1, which is twice that of pure NaNbO3(6.67µmol·g-1·h-1). This article highlights an impregnation method to build core-shell structures for improved photocatalytic reduction of CO2.

Coupling Direct Atmospheric CO2 Capture with Photocatalytic CO2 Reduction for Highly Efficient C2H6 Production.

As massive amounts of carbon dioxide (CO2) have been emitted into the atmosphere causing severe global warming problems, developing carbon-negative techniques to control atmospheric CO2 concentrations is enormously urgent. Herein, by coupling the direct atmosphere CO2 capture adsorbent ZSM-5 with the CO2 reduction photocatalyst NiV2Se4, we present the first synergistic approach for concentrating and converting atmospheric CO2 into C2 solar fuels. A C2H6 yield of 1.85 µmol g-1 h-1 has been achieved in the air, outperforming state-of-the-art direct atmospheric CO2 conversion photocatalysts. Comprehensive characterizations show that ZSM-5 enhances CO2 capture from the atmosphere, improving the interfacial interaction of CO2 on the NiV2Se4 surface for C-C coupling of CH3* to form C2H6. This work demonstrates the first example of integrating direct CO2 capture material with a CO2 reduction photocatalyst for atmospheric CO2 capture and utilization, which paves the way for the negative-carbon technology development under worldwide carbon-neutral pressure.

Doping Ferrocene-Based Conjugated Microporous Polymers with 7,7,8,8-Tetracyanoquinodimethane for Efficient Photocatalytic CO2 Reduction.

The design and synthesis of organic photocatalysts remain a great challenge due to their strict structural constraints. However, this could be mitigated by achieving structural flexibility by constructing permanent porosity into the materials. Conjugated microporous polymers (CMPs) are an emerging class of porous materials with an amorphous, three-dimensional network structure, which makes it possible to integrate the elaborate functional groups to enhance photocatalytic performance. Here, we report the synthesis of a novel CMP, named TAPFc-TFPPy-CMP, constructed by 1,1'3,3'-tetra(4-aminophenyl)ferrocene (TAPFc) and 1,3,6,8-tetrakis(4-formylphenyl)pyrene (TFPPy) monomers. The integration of the p-type dopant 7,7,8,8-tetracyanoquinodimethane (TCNQ) into the TAPFc-TFPPy-CMP improved the light adsorption performance, leading to a decrease in the optical bandgap from 2.00 to 1.43 eV. The doped CMP (TCNQ@TAPFc-TFPPy-CMP) exhibited promising catalytic activity in photocatalytic CO2 reduction under visible light, yielding 546.8 µmol g-1 h-1 of CO with a selectivity of 96% and 5.2 µmol g-1 h-1 of CH4. This represented an 80% increase in the CO yield compared to the maternal TAPFc-TFPPy-CMP. The steady-state photoluminescence (PL) and fluorescence lifetime (FL) measurements reveal faster carrier separation and transport after the doping. This study provides guidance for the development of organic photocatalysts for the utilization of renewable energy.