Efficient Photocatalytic Reduction Research Articles

Construction of three-coordinated (N3C) nitrogen vacancies in g-C3N4 for efficient photocatalytic CO2 reduction

Defect engineering has been widely applied in the field of photocatalysis, and defects can be used to modify the surface structure and photoelectric properties of catalysts so as to achieve the purpose of regulating the activity and stability of catalysts. However, design of a highly efficient photocatalyst with abundant defects remains a challenging task in current research. Therefore, in this study, graphitic carbon nitride (g-C3N4) with abundant three-coordinated nitrogen (N3C) vacancies and pore structures was obtained using a facile hydrothermal method with the assistance of glycerol. Under visible light (λ > 420 nm) irradiation, the 50CN (volume ratio of glycerol/water is 50/10) catalyst exhibits a superior CO release rate (4.18 μmol g−1 h−1), which is 12.06 times higher than the reference GCN (0.32 μmol g−1 h−1), and the corresponding apparent quantum yields (AQY) of 50CN is 0.24 %, which is significantly higher than that of GCN (0.045 %). Successful introduction of N3C vacancies is conducive to broaden light response range of the catalyst, enhancing the separation and migration efficiency of photogenerated charges, and providing more adsorption active sites to promote the adsorption and activation of CO2 molecules, thus effectively boosting photocatalytic CO2 reduction activity. In addition, the N3C vacancies can effectively lower the CO2 activation energy barrier and reduce the energy consumption required for the reaction. This work offers valuable new insights into defect engineering in g-C3N4 for the development of high-performance photocatalysts for CO2 reduction.

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.

Synergistic effect between ohmic contacts and localized surface plasmon resonance for enhancing CO2 photoreduction of BiOBr

The fast recombination rate of photogenerated carrier and short electron lifetime are the main factors affecting the CO2 reduction performance of BiOBr (BOB). The utilization of ohmic contacts and the localised surface plasmon resonance (LSPR) effect of metals can effectively solve the above problems. However, one mean alone is not ideal for improving the photocatalytic performance of BOB. Therefore, in this work, we reduced the metal Bi to the surface of BOB in an attempt to form a synergistic effect of ohmic contact and LSPR effect. DFT calculations confirm the ohmic contact between Bi and BOB. Meanwhile, electrochemical tests show that Bi/BOB-2 has a higher photocurrent density (1.1 μA/cm2), suggesting that the ohmic contact achieves ultrafast electron transfer from BOB to Bi under light. While the UV–Vis diffuse reflectance spectroscopy results show resonance absorption peaks from the LSPR effect of Bi, the TRPL results show that Bi/BOB-2 has a longer τave (3.05 ns), implying that longer-lived hot electrons are generated on the Bi surface. The synergistic effect of the two contributes to the efficient CO2 to CO transition on the catalyst surface. As a result, Bi/BOB-2 exhibites a 4.37-fold higher CO generation rate (11.45 μmolg-1 h−1) than that of pure BOB (2.62 μmolg-1 h−1) under light. This study provides a new blueprint for the design of BiOBr-based materials for efficient photocatalytic reduction of CO2.

Lewis acid-rich SrFexTi1−xO3/TiO2 to enhance the photocatalytic reduction of nitrate to N2

The photocatalytic reduction of nitrate has received considerable attention due to its high efficiency and environmentally friendly nature. The excessive addition of hole scavengers is the most commonly used method to increase the nitrate reduction efficiency. However, achieving high selectivity in the photocatalytic reduction of nitrate to N2 with low concentration of hole scavengers remains challenging. In this study, the SrFexTi1−xO3/TiO2 S-scheme heterojunction photocatalysts with many Lewis acidic adsorption sites have been developed. The experimental results demonstrated that the incorporation of 6% Fe into SrFe0.06Ti0.94O3/TiO2 (SFTO6) resulted in the nitrate conversion rate of 97.68% and the N2 selectivity reached 96.35% with 25 mmol/L formic acid. Moreover, it also exhibited excellent stability and recycle ability. After 5 cycles, SFTO6 still exhibited a stable photocatalytic denitration efficiency of 92.94%, highlighting its potential for practical application. Through comprehensive mechanistic investigations, enhancing direct reduction process is considered the key to its high reduction efficiency with low formic acid. And the Lewis acidic adsorption sites enhance N2 selectivity by enriching NOx− on the surface of the material. Overall, this study provides a novel approach for achieving efficient photocatalytic reduction of nitrate to N2 under conditions with low concentration of hole scavengers.

Engineering Built-In Electric Field Microenvironment of CQDs/g-C3N4 Heterojunction for Efficient Photocatalytic CO2 Reduction.

Graphitic carbon nitride (CN), as a nonmetallic photocatalyst, has gained considerable attention for its cost-effectiveness and environmentally friendly nature in catalyzing solar-driven CO2 conversion into valuable products. However, the photocatalytic efficiency of CO2 reduction with CN remains low, accompanied by challenges in achieving desirable product selectivity. To address these limitations, a two-step hydrothermal-calcination tandem synthesis strategy is presented, introducing carbon quantum dots (CQDs) into CN and forming ultra-thin CQD/CN nanosheets. The integration of CQDs induces a distinct work function with CN, creating a robust interface electric field after the combination. This electric field facilitates the accumulation of photoelectrons in the CQDs region, providing an abundant source of reduced electrons for the photocatalytic process. Remarkably, the CQD/CN nanosheets exhibit an average CO yield of 120µmol g-1, showcasing an outstanding CO selectivity of 92.8%. The discovery in the work not only presents an innovative pathway for the development of high-performance photocatalysts grounded in non-metallic CN materials employing CQDs but also opens new avenues for versatile application prospects in environmental protection and sustainable cleaning energy.

Asymmetric acceptor-donor-acceptor type covalent organic frameworks with dual O2 reduction moieties for boosting H2O2 photosynthesis

The study of hydrogen peroxide production by O2 reduction reaction using covalent organic framework (COF) photocatalysts has attracted extensive attention in recent years. However, there are still great challenges in accurately controlling their structures to achieve rapid carrier separation and efficient O2 reduction. Based on this, we constructed the A1-D-A2 COF photocatalytic material (TT-DTDA-COF) with asymmetric dual acceptor sites by connecting thieno [3,2-b] thiophene, benzene, and triazine as the basic units through imine bonds. Under the synergistic effect of thieno [3,2-b] thiophene and triazine electron acceptors, the separation and transfer efficiency of TT-DTDA-COF photogenerated carriers was significantly enhanced. At the same time, according to the in-situ infrared and DFT calculation results, it was found that these two acceptor units served as O2 reduction sites, which realized the multi-site adsorption reduction of O2, and effectively enhanced the efficiency of photocatalytic O2 reduction to H2O2. The experimental results showed that the H2O2 generation rate of TT-DTDA-COF with A1-D-A2 dual receptor structure was 1302 μmol·g−1·h−1 under visible light irradiation, which was 3.4 times higher than that of TB-DTDA-COF with single receptor D-A structure and higher than that of most of the materials reported so far. This study provides a new idea for accurately designing COF-based photocatalysts to achieve efficient O2 reduction to produce H2O2.

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.

Efficient photocatalytic CO2 reduction achieved by constructing Bi4O5Br2/Bi-MOF Z-scheme heterojunction

Building efficient catalysts is an urgent issue in the field of photocatalytic CO2 reduction, and Z-scheme heterojunction structures can availably suppress the recombination of photo generated carriers and improve photocatalytic performance. This study successfully prepared a new type of Bi4O5Br2/Bi-MOF composite photocatalyst through self-assembly method. After 5 h of simulated sunlight exposure, the optimized sample 50-Bi4O5Br2/Bi-MOF photocatalytic reduction of CO2 to CO efficiency (23.78 μmol·g−1·h−1) was 5.09 times higher than pure Bi4O5Br2, and the CH4 yield (5.39 μmol·g−1·h−1) was 2.52 times that of pure Bi-MOF. In addition, in the cyclic experiment, the catalyst had high stability and reusability. The Z-scheme charge transfer mechanism was confirmed through band structure analysis, Electron spin resonance (ESR), Ultraviolet photoelectron spectroscopy (UPS) and other related characterizations. This work provided an important strategy for designing efficient Z-scheme heterojunction photocatalysts.

Efficient photocatalytic reduction of Cr(VI) and degradation of tetracycline by Bi2Se3@ZnIn2S4 binary heterostructures enriched with sulfur vacancies: Mechanism and mineralization analysis

Constructing a sulfur-vacancy-enriched heterostructure offers advantages in enhancing photocatalytic performance due to the synergy between the vacancy’s electron-trapping and the internal electric field (IEF) features. In this study, a series of IEF-modulated type-I heterostructures containing sulfur vacancies-rich ZnIn2S4 (SV-ZIS) and Bi2Se3 (BSe) was rationally developed by hydrothermal and reduction methods. The optimized BSe@SV-ZIS catalyst shows an outstanding photocatalytic Cr(VI) reduction and tetracycline degradation rates, which are ∼ 2.1 and ∼ 1.5 times higher than that of pure SV-ZIS and BSe, respectively. Notably, the enhanced catalytic performance of binary samples could be linked to efficient absorption of the full spectrum of light, heterojunction formation and larger contact area to enhance the charge carriers movement at their interface and exceptional photo-stability. By assisting DRS, VB-XPS, and UPS analyses, details of the energy band position, charge carriers transport route, and preliminary photocatalytic mechanism were systematically explored. Furthermore, radical scavenging and electron paramagnetic resonance experiments were conducted to provide evidence of the participation of the reactive species during photocatalysis over BSe@SV-ZIS. Kinetic analysis revealed that the rate of photocatalytic process adheres to the Langmuir–Hinshelwood kinetic model. These results demonstrated that the heterostructuring approach holds significant potential as an effective avenue for developing photocatalysts that can harness both visible and NIR light, offering promising solutions to contemporary challenges in the realms of environmental decontamination and energy.

Ligand modulation of active center to promote lead-free Cs2AgInCl6 photocatalytic CO2 reduction

Metal halide perovskites (MHP) are potential candidates for the photocatalytic reduction of CO2 due to their long photogenerated carrier lifetime and charge diffusion length. However, the conventional long-chain ligand impedes the adsorption and activation of CO2 molecules in practical applications. Here, a ligand modulation technology is employed to enhance the photocatalytic CO2 reduction activity of lead-free Cs2AgInCl6 microcrystals (MCs). The Cs2AgInCl6 MCs passivated by Oleic acid (OLA) and Octanoic acid (OCA) are used for photocatalytic CO2 reduction. The results show that the surface defects and electronic properties of Cs2AgInCl6 MCs can be adjusted through ligand modulation. Compared with the OLA-Cs2AgInCl6, the OCA-Cs2AgInCl6 catalyst demonstrated a significant improvement in the catalytic yield of CO and CH4. The CO and CH4 catalytic yields of OCA-Cs2AgInCl6 reached 171.88 and 34.15 µmol g−1 h−1 which were 2.03 and 12.98 times higher than those of OLA- Cs2AgInCl6, and the total electron consumption rate of OCA-Cs2AgInCl6 was 615.2 µmol g−1 h−1 which was 3.25 times higher than that of OLA-Cs2AgInCl6. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs2AgInCl6 MCs induced by ligand modulation. This study illustrates the potential of lead-free Cs2AgInCl6 MCs for efficient photocatalytic CO2 reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Fe-TiO2-x/TiO2 S-scheme homojunction for efficient photocatalytic CO2 reduction

CO2-to-high value-added chemicals via a photocatalytic route is of interest but strangled by the low efficiency. Herein, a novel Fe-TiO2-x/TiO2 S-scheme homojunction was designed and constructed by using a facile surface modification approach whereby oxygen vacancy (OV) and Fe introducing on the TiO2 nanorod surface. The as-synthesized Fe-TiO2-x/TiO2 S-scheme homojunction exhibits positive properties on promoting photocatalytic CO2 reduction: i) the nanorod structure provides numerous active sites and a radical charge transfer path; ii) the doped Fe and OV not only synergistically enhance light utilization but also promote CO2 adsorption; iii) the Fe-TiO2-x/TiO2 S-scheme homojunction benefits photoexcited charge separation and retains stronger redox capacity. Thanks to those good characters, the Fe-TiO2-x/TiO2 homojunction exhibits superior CO2 reduction performances with optimized CO/CH4 generation rates of 122/22 μmol g-1h−1 which exceed those of pure TiO2 by more than 9.4/7.3 folds and most currently reported catalytic systems. This manuscript develops a facile and universal approach to synthesize well-defined homojunction and may inspire the construction of other more high-efficiency photocatalysts toward CO2 reduction and beyond.

Surface Coordination Environment Engineering on PtxCu1-x Alloy Catalysts for the Efficient Photocatalytic Reduction of CO2 to CH4.

Alloy catalysts have been reported to be robust in catalyzing various heterogeneous reactions due to the synergistic effect between different metal atoms. In this work, aimed at understanding the effect of the coordination environment of surface atoms on the catalytic performance of alloy catalysts, a series of PtxCu1-x alloy model catalysts supported on anatase-phase TiO2 (PtxCu1-x/Ti, x = 0.4, 0.5, 0.6, 0.8) were developed and applied in the classic photocatalytic CO2 reduction reaction. According to the results of catalytic performance evaluation, it was found that the photocatalytic CO2 reduction activity on PtxCu1-x/Ti showed a volcanic change as a function of the Pt/Cu ratio, the highest CO2 conversion was achieved on Pt0.5Cu0.5/Ti, with CH4 as the main product. Further systematic characterizations and theoretical calculations revealed that the equimolar amounts of Pt and Cu in Pt0.5Cu0.5/Ti facilitated the generation of more Cu-Pt-paired sites (i.e., the higher coordination number of Pt-Cu), which would favor a bridge adsorption configuration of CO2 and facilitate the electron transfer, thus resulting in the highest photocatalytic CO2 reduction efficiency on Pt0.5Cu0.5/Ti. This work provided new insights into the design of excellent CO2 reduction photocatalysts with high CH4 selectivity from the perspective of surface coordination environment engineering on alloy catalysts.

Construction of TiO2/CuPc Heterojunctions for the Efficient Photocatalytic Reduction of CO2 with Water.

Utilizing solar energy for photocatalytic CO2 reduction is an attractive research field because of its convenience, safety, and practicality. The selection of an appropriate photocatalyst is the key to achieve efficient CO2 reduction. Herein, we report the synthesis of TiO2/CuPc heterojunctions by compositing CuPc with TiO2 microspheres via a hydroxyl-induced self-assembly process. The experimental investigations demonstrated that the optimal TiO2/0.5CuPc photocatalyst exhibited a significantly enhanced CO2 photoreduction rate up to 32.4 μmol·g-1·h-1 under 300 W xenon lamp irradiation, which was 3.7 times that of the TiO2 microspheres alone. The results of photoelectrochemical experiments indicated that the construction of the heterojunctions by introducing CuPc effectively promoted the separation and transport of photogenerated carriers, thus enhancing the catalytic effect of the photocatalyst.

Thiazole-functionalized conjugated microporous polymers enable efficient gold recovery from e-waste

From the perspectives of environmental protection and efficiency, the use of clean and efficient photocatalytic reduction technology to recover gold from e-waste not only has a high economic value, but also reduces environmental pollution. However, it remains a challenge to construct adsorbents with simultaneously high photocatalytic activity, high stability, high capacity and high selectivity. Here, we demonstrate the application of D-π-A type thiazole-functionalized conjugated microporous polymer (termed BTD-TEA) for adsorption-photocatalytic recovery of gold from e-waste. The synthesized BTD-TEA not only have a narrow optical bandgap (1.75 eV) and excellent semiconductor properties, but also have ultra-high acid stability (stable in aqua regia). Surprisingly, BTD-TEA exhibits breakthrough gold adsorption capacity (4052.83 mg g−1), ultrafast adsorption kinetics, excellent selectivity and outstanding reusability under light conditions. This work provides a promising new adsorption-photocatalytic strategy for gold recovery from e-waste.

Microwave-assisted fabrication of 1D/2D CeO2/Bi2MoO6 heterojunction for efficient photocatalytic CO2 reduction to CH3OH

Photocatalytic CO2 reduction to fuels via visible light is regarded as a highly promising sustainable technology to address resource depletion and environmental apprehensions. However, the elevation of photocatalytic performance is limited due to some drawbacks of isolated catalysts such as poor CO2 adsorption performance, inadequate utilization of visible light, and rapid recombination of photo-generated carriers. Herein, a series of novel heterojunction catalysts, 1D/2D CeO2/Bi2MoO6 (CBMO-X), were fabricated utilizing the microwave-assisted method for the photocatalytic reduction of CO2. The CH3OH yield of the optimized CBMO-10 composite material reached 4.31 μmol⋅g−1⋅h−1 with excellent stability and structural integrity. Through a series of characterizations, it was found that the introduced CeO2 nanorods served as bifunctional sites for CO2 adsorption and photoelectron accumulation, effectively promoting CO2 conversion under visible light. In addition, CBMO-X exhibited faster photo-generated carriers migration rate due to the formation of the II-scheme heterojunction, which improved the photocatalytic performance obviously. Furthermore, the density functional theory (DFT) calculations and in situ XPS were used to investigate the carrier migration paths on the surface of composite materials. This work provided a novel strategy for the design of photocatalysts for efficient CO2 conversion.

Photocatalytic manipulation of Ca2+ signaling for regulating cellular and animal behaviors via MOF-enabled H2O2 generation.

The in situ generation of H2O2 in cells in response to external stimulation has exceptional advantages in modulating intracellular Ca2+ dynamics, including high controllability and biological safety, but has been rarely explored. Here, we develop photocatalyst-based metal-organic frameworks (DCSA-MOFs) to modulate Ca2+ responses in cells, multicellular spheroids, and organs. By virtue of the efficient photocatalytic oxygen reduction to H2O2 without sacrificial agents, photoexcited DCSA-MOFs can rapidly trigger Ca2+ outflow from the endoplasmic reticulum with single-cell precision in a repeatable and controllable manner, enabling the propagation of intercellular Ca2+ waves (ICW) over long distances in two-dimensional and three-dimensional cell cultures. After photoexcitation, ICWs induced by DCSA-MOFs can activate neural activities in the optical tectum of tadpoles and thighs of spinal frogs, eliciting the corresponding motor behaviors. Our study offers a versatile optical nongenetic modulation technique that enables remote, repeatable, and controlled manipulation of cellular and animal behaviors.

Construction of Bi2O3−x/NiAl-LDH S-scheme heterojunction for boosting photothermal-assisted photocatalytic CO2 reduction

In this study, a new type of 2D/2D Bi2O3−x/NiAl-LDH (BO/NA-LDH) S-scheme photocatalyst was prepared by combining NiAl-LDH with Bi2O3−x by wet chemical deposition for obtaining efficient photothermal-assisted photocatalytic reduction of CO2 under simulated sunlight irradiation. In particular, the as-prepared optimal 50-BO/NA-LDH sample exhibited the CO production yield of 83.55 ± 2.76 μmol/g/h, which was 9 and 27 times that of BO (9.32 ± 0.62 μmol/g/h) and NA-LDH (3.09 ± 0.38 μmol/g/h), respectively. The enhancement of photothermal-assisted activity over the 50-BO/NA-LDH system was mainly attributed to the coupling of the photothermal conversion performance of Bi2O3−x and improving the migration efficiency of interface carriers of S-scheme heterojunction and 2D/2D structure. This study presents a promising strategy for the development of high-efficient photothermal-assisted photocatalysts.

Engineering ZIF-67 loaded nanofibrous membrane with thermal stabilization treatment for efficient photocatalytic CO2 reduction

The photocatalytic Metal-organic frameworks (MOFs) membrane addresses challenges faced by MOF powders in practical applications such as aggregation and difficult recovery, but its current application is mainly confined to wastewater treatment. Expanding the application of MOFs membranes to CO2 reduction could unleash their greater potential in energy conversion and storage field. In this study, ZIF-67 was deposited on polyacrylonitrile (PAN) nanofiber membranes (NFMs) using an in-situ growth technique, followed by thermal stabilization to produce SZIF-67/PAN NFMs for photocatalytic CO2 reduction. ZIF-67 was uniformly and densely distributed on the NFMs, with a mass loading of up to 8 wt%. The thermal stabilization process significantly enhanced the photothermal conversion capability and solvent resistance of the NFMs, enabling SZIF-67/PAN NFMs to exhibit outstanding photocatalytic activity even under mild environmental conditions, with a remarkable CO generation rate of 39,250 μmol g−1h−1. Furthermore, the performance remained at 70 % even after five consecutive tests. This study presents a novel and effective method for preparing MOF NFMs with excellent photocatalytic CO2 reduction performance, offering valuable insights for advancing the practical application of MOF materials.

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.

Boron-Nitrogen-Embedded Polycyclic Aromatic Hydrocarbon-Based Controllable Hierarchical Self-Assemblies through Synergistic Cation-π and C-H···π Interactions for Bifunctional Photo- and Electro-Catalysis.

Boron-Nitrogen-embedded polycyclic aromatic hydrocarbons (BN-PAHs) as novel π-conjugated systems have attracted immense attention owing to their superior optoelectronic properties. However, constructing long-range ordered supramolecular assemblies based on BN-PAHs remains conspicuously scarce, primarily attributed to the constraints arising from coordinating multiple noncovalent interactions and the intrinsic characteristics of BN-PAHs, which hinder precise control over delicate self-assembly processes. Herein, we achieve the successful formation of BN-PAH-based controllable hierarchical assemblies through synergistically leveraged cation-π and C-H···π interactions. By carefully adjusting the solvent conditions in two progressive assembly hierarchies, the one-dimensional (1D) supramolecular assemblies with "rigid yet flexible" assembled units are first formed by cation-π interactions, and then they can be gradually fused into two-dimensional (2D) structures under specific C-H···π interactions, thus realizing the precise control of the transformation process from BN-PAH-based 1D primary structures to 2D higher-order assemblies. The resulting 2D-BNSA, characterized by enhanced electrical conductivity and ordered 2D layered structure, provides anchoring and dispersion sites for loading two appropriate nanocatalysts, thus facilitating the efficient photocatalytic CO2 reduction (with a remarkable CH4 evolution rate of 938.7 μmol g-1 h-1) and electrocatalytic acetylene semihydrogenation (reaching a Faradaic efficiency for ethylene up to 98.5%).