Isomeric Oligo(Phenylenevinylene)-Based Covalent Organic Frameworks with Different Orientation of Imine Bonds and Distinct Photocatalytic Activities

Imine-linked covalent organic frameworks (COFs) have been extensively studied in photocatalysis because of their easy synthesis and excellent crystallinity. The effect of imine-bond orientation on the photocatalytic properties of COFs, however, is still rarely studied. Herein, we report two novel COFs with different orientations of imine bonds using oligo(phenylenevinylene) moieties. The COFs showed similar structures but great differences in their photoelectric properties. COF-932 demonstrated a superior hydrogen evolution performance compared to COF-923 when triethanolamine was used as the sacrificial agent. Interestingly, the use of ascorbic acid led to the protonation of the COFs, further altering the direction of electron transfer. The photocatalytic performances were increased to 23.4 and 0.73 mmol g⁻¹ h⁻¹ for protonated COF-923 and COF-932, respectively. This study provides a clear strategy for the design of imine-linked COF-based photocatalysts and advances the development of COFs.     

Enhancement of Visible-Light-Driven Hydrogen Evolution Activity of 2D π-Conjugated Bipyridine-Based Covalent Organic Frameworks via Post-Protonation

Photocatalytic hydrogen (H₂) evolution represents a promising and sustainable technology. Covalent organic frameworks (COFs)-based photocatalysts have received growing attention. A 2D fully conjugated ethylene-linked COF (BTT-BPy-COF) was fabricated with a dedicated designed active site. The introduced bipyridine sites enable a facile post-protonation strategy to fine-tune the actives sites, which results in a largely improved charge-separation efficiency and increased hydrophilicity in the pore channels synergically. After modulating the degree of protonation, the optimal BTT-BPy-PCOF exhibits a remarkable H₂ evolution rate of 15.8 mmol g⁻¹ h⁻¹ under visible light, which surpasses the biphenyl-based COF 6 times. By using different types of acids, the post-protonation is proved to be a potential universal strategy for promoting photocatalytic H₂ evolution. This strategy would provide important guidance for the design of highly efficient organic semiconductor photocatalysts.     

Semiconductor/Covalent-Organic-Framework Z-Scheme Heterojunctions for Artificial Photosynthesis

A strategy to covalently connect crystalline covalent organic frameworks (COFs) with semiconductors to create stable organic–inorganic Z-scheme heterojunctions for artificial photosynthesis is presented. A series of COF–semiconductor Z-scheme photocatalysts combining water-oxidation semiconductors (TiO₂, Bi₂WO₆, and α-Fe₂O₃) with CO₂ reduction COFs (COF-316/318) was synthesized and exhibited high photocatalytic CO₂-to-CO conversion efficiencies (up to 69.67 μmol g⁻¹ h⁻¹), with H₂O as the electron donor in the gas–solid CO₂ reduction, without additional photosensitizers and sacrificial agents. This is the first report of covalently bonded COF/inorganic-semiconductor systems utilizing the Z-scheme applied for artificial photosynthesis. Experiments and calculations confirmed efficient semiconductor-to-COF electron transfer by covalent coupling, resulting in electron accumulation in the cyano/pyridine moieties of the COF for CO₂ reduction and holes in the semiconductor for H₂O oxidation, thus mimicking natural photosynthesis.     

Regulating Relative Nitrogen Locations of Diazine Functionalized Covalent Organic Frameworks for Overall H2O2 Photosynthesis

Nitrogen-heterocycle-based covalent organic frameworks (COFs) are considered promising candidates for the overall photosynthesis of hydrogen peroxide (H₂O₂). However, the effects of the relative nitrogen locations remain obscured and photocatalytic performances of COFs need to be further improved. Herein, a collection of COFs functionalized by various diazines including pyridazine, pyrimidine, and pyrazine have been judiciously designed and synthesized for photogeneration of H₂O₂ without sacrificial agents. Compared with pyrimidine and pyrazine, pyridazine embedded in TpDz tends to stabilize endoperoxide intermediate species, leading toward the more efficient direct 2e^- oxygen reduction reaction (ORR) pathway. Benefiting from the effective electron-hole separation, low charge transfer resistance, and high-efficiency ORR pathway, an excellent production rate of 7327 μmol g⁻¹ h⁻¹ and a solar-to-chemical conversion (SCC) value of 0.62 % has been achieved by TpDz, which ranks one of the best COF-based photocatalysts. This work might shed fresh light on the rational design of functional COFs targeting photocatalysts in H₂O₂ production.     

Hot π‐Electron Tunneling of Metal–Insulator–COF Nanostructures for Efficient Hydrogen Production

A metal–insulator–semiconductor (MIS) photosystem based on covalent organic framework (COF) semiconductors was designed for robust and efficient hydrogen evolution under visible‐light irradiation. A maximal H₂ evolution rate of 8.42 mmol h^?1 g^?1 and a turnover frequency of 789.5 h^?1 were achieved by using a MIS photosystem prepared by electrostatic self‐assembly of polyvinylpyrrolidone (PVP) insulator‐capped Pt nanoparticles (NPs) with the hydrophilic imine‐linked TP‐COFs having =C=O?H?N= hydrogen‐bonding groups. The hot π‐electrons in the photoexcited n‐type TP‐COF semiconductors can be efficiently extracted and tunneled to Pt NPs across an ultrathin PVP insulating layer to reduce protons to H₂. Compared to the Schottky‐type counterparts, the COF‐based MIS photosystems give a 32‐fold‐enhanced carrier efficiency, attributed to the combined enhancement of photoexcitation rate, charge separation, and oxidation rate of holes accumulated in the valence band of the TP‐COF semiconductor.     

An Amine-Functionalized Zirconium Metal–Organic Polyhedron Photocatalyst with High Visible-Light Activity for Hydrogen Production

Metal–organic polyhedra (MOPs) are promising candidates for many potential applications; however, their use as photocatalysts for hydrogen production has yet to be developed. Herein, the photocatalytic performance of a water-stable Zr-MOP, ZrT-1-NH₂, was evaluated, for the first time, through photocatalytic hydrogen evolution under visible-light irradiation. ZrT-1-NH₂ shows clearly enhanced photocatalytic activity (510.42 μmol g⁻¹ h⁻¹) for hydrogen production, in comparison with that of other homogeneous crystalline materials. If platinum nanoparticles were introduced into the photocatalytic system, the hydrogen production efficiency of ZrT-1-NH₂ could be further improved. For ZrT-1-NH₂, the conspicuous improvement in photocatalysis can be attributed to efficient electron–hole separation, targeted electron transfer, and excellent recombination suppression. Furthermore, ZrT-1-NH₂ shows excellent stability during photocatalytic hydrogen evolution over five continuous runs. This work illustrates that MOP-based photocatalysts hold promise for broad applications in the domain of clean energy.     

Realizing high hydrogen evolution activity under visible light using narrow band gap organic photocatalysts

The design and synthesis of conjugated semiconducting polymers for photocatalytic hydrogen evolution have engendered intense recent interest. However, most reported organic polymer photocatalysts show a relatively broad band gap with weak light absorption ability in the visible light region, which commonly leads to a low photocatalytic activity under visible light. Herein, we synthesize three novel dithieno[3,2-b:2′,3′-d]thiophene-S,S-dioxide (DTDO) containing conjugated polymer photocatalysts by a facile C–H arylation coupling polymerization reaction. The resulting polymers show a broad visible light absorption range up to 700 nm and a narrow band gap down to 1.81 eV due to the introduction of the DTDO unit. Benefiting from the donor–acceptor polymer structure and the high content of the DTDO unit, the three-dimensional polymer PyDTDO-3 without the addition of a Pt co-catalyst shows an attractive photocatalytic hydrogen evolution rate of 16.32 mmol h⁻¹ g⁻¹ under visible light irradiation, which is much higher than that of most reported organic polymer photocatalysts under visible light.

Narrow band gap conjugated polymer photocatalysts containing dithieno[3,2-b:2′,3′-d]thiophene-S,S-dioxide show an attractive photocatalytic hydrogen evolution rate of 16.32 mmol h⁻¹ g⁻¹ under visible light irradiation.     

Strong-Base-Assisted Synthesis of a Crystalline Covalent Triazine Framework with High Hydrophilicity via Benzylamine Monomer for Photocatalytic Water Splitting

Methods to synthesize crystalline covalent triazine frameworks (CTFs) are limited and little attention has been paid to development of hydrophilic CTFs and photocatalytic overall water splitting. A route to synthesize crystalline and hydrophilic CTF-HUST-A1 with a benzylamine-functionalized monomer is presented. The base reagent used plays an important role in the enhancement of crystallinity and hydrophilicity. CTF-HUST-A1 exhibits good crystallinity, excellent hydrophilicity, and excellent photocatalytic activity in sacrificial photocatalytic hydrogen evolution (hydrogen evolution rate up to 9200 μmol g⁻¹ h⁻¹). Photocatalytic overall water splitting is achieved by depositing dual co-catalysts in CTF-HUST-A1, with H₂ evolution and O₂ evolution rates of 25.4 μmol g⁻¹ h⁻¹ and 12.9 μmol g⁻¹ h⁻¹ in pure water without using sacrificial agent.     

Isolated Electron Trap-Induced Charge Accumulation for Efficient Photocatalytic Hydrogen Production

The solar-driven evolution of hydrogen from water using particulate photocatalysts is considered one of the most economical and promising protocols for achieving a stable supply of renewable energy. However, the efficiency of photocatalytic water splitting is far from satisfactory due to the sluggish electron-hole pair separation kinetics. Herein, isolated Mo atoms in a high oxidation state have been incorporated into the lattice of Cd_0.5Zn_0.5S (CZS@Mo) nanorods, which exhibit photocatalytic hydrogen evolution rate of 11.32 mmol g⁻¹ h⁻¹ (226.4 μmol h⁻¹; catalyst dosage 20 mg). Experimental and theoretical simulation results imply that the highly oxidized Mo species lead to mobile-charge imbalances in CZS and induce the directional photogenerated electrons transfer, resulting in effectively inhibited electron-hole recombination and greatly enhanced photocatalytic efficiency.     

The Keto-Switched Photocatalysis of Reconstructed Covalent Organic Frameworks for Efficient Hydrogen Evolution

The keto-switched photocatalysis of covalent organic frameworks (COFs) for efficient H₂ evolution was reported for the first time by engineering, at a molecular level, the local structure and component of the skeletal building blocks. A series of imine-linked BT-COFs were synthesized by the Schiff-base reaction of 1, 3, 5-benzenetrialdehyde with diamines to demonstrate the structural reconstruction of enol to keto configurations by alkaline catalysis. The keto groups of the skeletal building blocks served as active injectors, where hot π-electrons were provided to Pt nanoparticles (NPs) across a polyvinylpyrrolidone (PVP) insulting layer. The characterization results, together with density functional theory calculations, indicated clearly that the formation of keto-injectors not only made the conduction band level more negative, but also led to an inhomogeneous charge distribution in the donor-acceptor molecular building blocks to form a strong intramolecular built-in electric field. As a result, visible-light photocatalysis of TP-COFs-1 with one keto group in the skeletal building blocks was successfully enabled and achieved an impressive H₂ evolution rate as high as 0.96 mmol g⁻¹ h⁻¹. Also, the photocatalytic H₂ evolution rates of the reconstructed BT-COFs-2 and -3 with two and three keto-injectors were significantly enhanced by alkaline post-treatment.     

Highly-Active Chiral Organic Photovoltaic Catalysts with Suppressed Charge Recombination

Recombination of free charges in organic semiconductors reduces the available photo-induced charge-carriers and restricts photovoltaic efficiency. In this work, the chiral organic semiconductors (Y6-R and Y6-S with enantiopure R- and S- chiral alkyl sidechains) are designed and synthesized, which show effective aggregation-induced chirality through mainchain packing with chiral conformations in non-centrosymmetric space groups with tilt chirality. Based on the analysis of spin-injection, magnetic-hysteresis loop, and thermodynamics and dynamics of the excited state, we suggest that the aggregation-induced chirality can generate spin-polarization, which suppresses charge recombination and offers more available charge-carriers within Y6-R and Y6-S relative to the achiral counterpart (Y6). Then the chiral Y6-R and Y6-S show enhanced catalytic activity with optimal average hydrogen evolution rates of 205 and 217 mmol h⁻¹ g⁻¹, respectively, 60–70 % higher than Y6, when they are employed as nanoparticle photocatalysts in photocatalytic hydrogen evolution under simulated solar light, AM1.5G, 100 mW cm⁻².     

Multicomponent Synthesis of Imidazole-Linked Fully Conjugated 3D Covalent Organic Framework for Efficient Electrochemical Hydrogen Peroxide Production

The semiconducting properties and applications of three dimensional (3D) covalent organic frameworks (COFs) are greatly hampered because of their long-ranged non-conjugated skeletons and relatively unstable linkages. Here, a robust imidazole-linked fully conjugated 3D covalent organic framework (BUCT-COF-7) is synthesized through the one-pot multicomponent Debus-Radziszewski reaction of the saddle-shaped aldehyde-substituted cyclooctatetrathiophene, pyrene-4,5,9,10-tetraone, and ammonium acetate. The semiconducting BUCT-COF-7, as a metal-free catalyst, shows excellent two electron oxygen reduction reaction (ORR) activity in alkaline medium with high hydrogen peroxide (H₂O₂) selectivity of 83.4 %. When the BUCT-COF-7 as cathode catalyst is assembled into the electrolyzer, the devices showed high electrochemical production rate of H₂O₂ up to 326.9 mmol g⁻¹ h⁻¹. The accumulative amount of H₂O₂ could totally degrade the dye methylene blue via Fenton reaction for wastewater treatment. This is the first report about intrinsic 3D COFs for efficient electrochemical synthesis of H₂O₂, revealing the promising applications of fully conjugated 3D COFs in the environment-related field.     

Value Added Conversion of Ethanol on Morphologically Controlled and Defect-Engineered Titanium Dioxide Nanorods

Developing an environmentally benign and highly effective strategy for the value-added conversion of biomass platform molecules such as ethanol has emerged as a significant challenge and opportunity. This challenge stems from the need to harness renewable solar energy and conduct thermodynamically unfavorable reactions at room temperature. To tackle this challenge, one-dimensional titanium dioxide photocatalysts have been designed and fabricated to achieve a remarkable photocatalytic selectivity of almost 100 % for transforming ethanol into value-added 1,1-diethoxyethane, contrasting the primary production of acetaldehyde in titanium dioxide nanoparticles. By incorporating a Pt co-catalyst and infusing oxygen vacancies into the one-dimensional catalyst, the ethanol transformation rate was doubled to 128.8 mmol g⁻¹ h⁻¹ with respect to that of its unmodified counterpart (about 66.7 mmol g⁻¹ h⁻¹). The underlying mechanism for this high conversion and selectivity resides in the narrowed bandgap of the catalyst and the prolonged lifetime of the photo-generated carriers. This is a promising strategy for the photocatalytic transformation of essential biomass platform molecules that intertwines morphological control and defect engineering.     

Enhancing Built-in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C60 Fullerene into Zirconium-Based Metal-Organic Frameworks

High-efficiency photocatalysts based on metal-organic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C₆₀ into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in C₆₀@NU-901. The direct consequence is a robust built-in electric field, which tends to be 10.7 times higher in C₆₀@NU-901 than that found in NU-901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g⁻¹ h⁻¹ for C₆₀@NU-901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host-guest interactions constitutes a promising strategy to design photocatalysts for efficient solar-to-chemical energy conversion.     

Engineering a Self-Grown TiO2/Ti-MOF Heterojunction with Selectively Anchored High-Density Pt Single-Atomic Cocatalysts for Efficient Visible-Light-Driven Hydrogen Evolution

A photocatalyst TiO₂/Ti-BPDC-Pt is developed with a self-grown TiO₂/Ti-metal–organic framework (MOF) heterojunction, i.e., TiO₂/Ti-BPDC, and selectively anchored high-density Pt single-atomic cocatalysts on Ti-BPDC for photocatalytic hydrogen evolution. This intimate heterojunction, growing from the surface pyrolytic reconstruction of Ti-BPDC, works in a direct Z-scheme, efficiently separating electrons and holes. Pt is selectively anchored on Ti-BPDC by ligands and is found in the form of single atoms with loading up to 1.8 wt %. The selective location of Pt is the electron-enriched domain of the heterojunction, which further enhances the utilization of the separated electrons. This tailored TiO₂/Ti-BPDC-Pt shows a significantly enhanced activity of 12.4 mmol g⁻¹ h⁻¹ compared to other TiO₂- or MOF-based catalysts. The structure-activity relationship further proves the balance of two simultaneously exposed domains of heterojunctions is critical to fulfilling this kind of catalyst.     

Covalent organic frameworks with imine proton acceptors for efficient photocatalytic H2 production

Covalent organic frameworks (COFs) are promising crystalline materials for the light-driven hydrogen evolution reaction (HER) due to their tunable chemical structures and energy band gaps. However, deeply understanding corresponding mechanism is still challenging due to the multiple components and complicated electron transfer and reduction paths involved in photocatalytic HER. Here, the photocatalytic HER investigation has been reported based on three COFs catalysts, 1–3, which are prepared by benzo[1,2-b:3,4-b':5,6-b']trithiophene-2,5,8-trialdehyde to react with C₃ symmetric triamines including tris(4-aminophenyl)amine, 1,3,5-tris(4-aminophenyl)benzene, and (1,3,5-tris-(4-aminophenyl)triazine, respectively. As the isostructural hexagonal honeycomb-type COF of 2 and 3 reported previously, the crystal structure of 1 has been carefully correlated through the powder X-ray diffraction study with the help of theoretical simulations. 1 shows highly porous framework with Brunauer-Emmett-Teller surface area of 1249 m²/g. Moreover, the introduction of ascorbic acid into the photocatalytic system of COFs achieves the hydrogen evolution rate of 3.75, 12.16 and 20.2 mmol g^–1 h^–1 for 1–3, respectively. The important role of ascorbic acid in photocatalysis of HER is disclosed to protonate the imine linkages of these COFs, leading to the obvious absorbance red-shift and the improved charge separation efficiency together with reduced resistance in contrast to pristine materials according to the spectroscopic and electronic characterizations. These innovations of chemical and physical properties for these COFs are responsible for their excellent photocatalytic performance. These results elucidate that tiny modifications of COFs structures is able to greatly tune their band structures as well as catalytic properties, therefore providing an available approach for optimizing COFs functionalities.     

Stable Immobilization of Nickel Ions on Covalent Organic Frameworks for Panchromatic Photocatalytic Hydrogen Evolution

Post-coordination design on covalent organic frameworks (COFs) is an efficient strategy for elevating the photocatalytic activity of organic moiety. However, the rigid skeletons and densely layered stacking of two-dimensional (2D) COFs cannot be flexibly adapted for specific conformations of metal complexes, thereby impairing the metal-COF cooperation. Here, we adopt a solvothermal method to immobilize nickel(II) ions into a 2,2′-bipyridine-containing 2D COF, forming a stable coordination motif. Such the complex remarkably enhances the photocatalytic performance, giving an optimized H₂ evolution rate of as high as 51 300 μmol h⁻¹ g⁻¹, 2.5 times higher than the pristine COF. The evolved hydrogen gas can also be detected upon 700-nm light irradiation, while its analog synthesized by the traditional coordination method is photo-catalytically inert. This work provides a strategy for optimizing the metal-COF coordination system and strengthening a synergy for electronic regulation in photocatalysis.     

Organic Photovoltaic Catalyst with σ-π Anchor for High-Performance Solar Hydrogen Evolution

Efficient in situ deposition of metallic cocatalyst, like zero-valent platinum (Pt), on organic photovoltaic catalysts (OPCs) is the prerequisite for their high catalytic activities. Here we develop the OPC (Y6CO), by introducing carbonyl in the core, which is available to σ-π coordinate with transition metals, due to the high-energy empty π* orbital of carbonyl. Y6CO exhibits a stronger capability to anchor Pt species and reduce them to metallic state, resulting in more Pt⁰ deposition, relative to the control OPC without the central σ-π anchor. Single-component and heterojunction nanoparticles (NPs) employing Y6CO show enhanced average hydrogen evolution rates of 230.98 and 323.22 mmol h⁻¹ g_[OPC]⁻¹, respectively, under AM 1.5G, 100 mW cm⁻² for 10 h, and heterojunction NPs yield the external quantum efficiencies of ca. 10 % in 500–800 nm. This work demonstrates that σ-π anchoring is one efficient strategy for integrating metallic cocatalyst and OPC for high-performance photocatalysis.     

Direct Observation of Dynamic Bond Evolution in Single-Atom Pt/C3N4 Catalysts

Single-atom catalysts are promising platforms for heterogeneous catalysis, especially for clean energy conversion, storage, and utilization. Although great efforts have been made to examine the bonding and oxidation state of single-atom catalysts before and/or after catalytic reactions, when information about dynamic evolution is not sufficient, the underlying mechanisms are often overlooked. Herein, we report the direct observation of the charge transfer and bond evolution of a single-atom Pt/C₃N₄ catalyst in photocatalytic water splitting by synchronous illumination X-ray photoelectron spectroscopy. Specifically, under light excitation, we observed Pt−N bond cleavage to form a Pt⁰ species and the corresponding C=N bond reconstruction; these features could not be detected on the metallic platinum-decorated C₃N₄ catalyst. As expected, H₂ production activity (14.7 mmol h⁻¹ g⁻¹) was enhanced significantly with the single-atom Pt/C₃N₄ catalyst as compared to metallic Pt-C₃N₄ (0.74 mmol h⁻¹ g⁻¹).     

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2O2

The full reaction photosynthesis of H₂O₂ that can combine water-oxidation and oxygen-reduction without sacrificial agents is highly demanded to maximize the light-utilization and overcome the complex reaction-process of anthraquinone-oxidation. Here, a kind of oxidation-reduction molecular junction covalent-organic-framework (TTF-BT-COF) has been synthesized through the covalent-coupling of tetrathiafulvalene (photo-oxidation site) and benzothiazole (photo-reduction site), which presents visible-light-adsorption region, effective electron-hole separation-efficiency and photo-redox sites that enables full reaction generation of H₂O₂. Specifically, a record-high yield (TTF-BT-COF, ≈276 000 μM h⁻¹ g⁻¹) for H₂O₂ photosynthesis without sacrificial agents has been achieved among porous crystalline photocatalysts. This is the first work that can design oxidation-reduction molecular junction COFs for full reaction photosynthesis of H₂O₂, which might extend the scope of COFs in H₂O₂ production.