Redox Molecular Junction Metal-Covalent Organic Frameworks for Light-assisted CO2 Energy Storage.

Visible-light sensitive and bi-functionally favored CO2 reduction (CRR)/evolution (CER) photocathode catalysts that can get rid of the utilization of ultraviolet light and improve sluggish kinetics is demanded to conquer the current technique-barrier of traditional Li-CO2 battery. Here, a kind of redox molecular junction sp2c metal-covalent organic framework (i.e. Cu3-BTDE-COF) has been prepared through the connection between Cu3 and BTDE and can serve as efficient photocathode catalyst in light-assisted Li-CO2 battery. Cu3-BTDE-COF with redox-ability, visible-light-adsorption region, electron-hole separation ability and endows the photocathode with excellent round-trip efficiency (95.2 %) and an ultralow voltage hysteresis (0.18 V), outperforming the Schiff base COFs (i.e. Cu3-BTDA-COF and Cu3-DT-COF) and majority of the reported photocathode catalysts. Combined theoretical calculations with characterizations, Cu3-BTDE-COF with the integration of Cu3 centers, thiazole and cyano groups possess strong CO2 adsorption/activation and Li+ interaction/diffusion ability to boost the CRR/CER kinetics and related battery property.

Modulated Connection Modes of Redox Units in Molecular Junction Covalent Organic Frameworks for Artificial Photosynthetic Overall Reaction.

The precise tuning of components, spatial orientations, or connection modes for redox units is vital for gaining deep insight into efficient artificial photosynthetic overall reaction, yet it is still hard achieve for heterojunction photocatalysts. Here, we have developed a series of redox molecular junction covalent organic frameworks (COFs) (M-TTCOF-Zn, M = Bi, Tri, and Tetra) for artificial photosynthetic overall reaction. The covalent connection between TAPP-Zn and multidentate TTF endows various connection modes between water photo-oxidation (multidentate TTF) and CO2 photoreduction (TAPP-Zn) centers that can serve as desired platforms to study the possible interactions between redox centers. Notably, Bi-TTCOF-Zn exhibits a high CO production rate of 11.56 µmol g-1 h-1 (selectivity, ∼100%), which is more than 2 and 6 times higher than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn, respectively. As revealed by theoretical calculations, Bi-TTCOF-Zn facilitates a more uniform distribution of energy-level orbitals, faster charge transfer, and stronger *OH adsorption/stabilization ability than those of Tri-TTCOF-Zn and Tetra-TTCOF-Zn.

Oxidation-Reduction Molecular Junction Covalent Organic Frameworks for Full Reaction Photosynthesis of H2 O2.

The full reaction photosynthesis of H2 O2 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 H2 O2 . Specifically, a record-high yield (TTF-BT-COF, ≈276 000 µM h-1 g-1 ) for H2 O2 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 H2 O2 , which might extend the scope of COFs in H2 O2 production.

Regulation of Redox Molecular Junctions in Covalent Organic Frameworks for H2 O2 Photosynthesis Coupled with Biomass Valorization.

H2 O2 photosynthesis coupled with biomass valorization can not only maximize the energy utilization but also realize the production of value-added products. Here, a series of COFs (i.e. Cu3 -BT-COF, Cu3 -pT-COF and TFP-BT-COF) with regulated redox molecular junctions have been prepared to study H2 O2 photosynthesis coupled with furfuryl alcohol (FFA) photo-oxidation to furoic acid (FA). The FA generation efficiency of Cu3 -BT-COF was found to be 575 mM g-1 (conversion ≈100 % and selectivity >99 %) and the H2 O2 production rate can reach up to 187 000 µM g-1 , which is much higher than Cu3 -pT-COF, TFP-BT-COF and its monomers. As shown by theoretical calculations, the covalent coupling of the Cu cluster and the thiazole group can promote charge transfer, substrate activation and FFA dehydrogenation, thus boosting both the kinetics of H2 O2 production and FFA photo-oxidation to increase the efficiency. This is the first report about COFs for H2 O2 photosynthesis coupled with biomass valorization, which might facilitate the exploration of porous-crystalline catalysts in this field.

Confining and Highly Dispersing Single Polyoxometalate Clusters in Covalent Organic Frameworks by Covalent Linkages for CO2 Photoreduction.

Single clusters have attracted extensive research interest in the field of catalysis. However, achieving a highly uniform dispersion of a single-cluster catalyst is challenging. In this work, for the first time, we present a versatile strategy for uniformly dispersed polyoxometalates (POMs) in covalent organic frameworks (COFs) through confining POM cluster into the regular nanopores of COF by a covalent linkage. These COF-POM composites combine the properties of light absorption, electron transfer, and suitable catalytic active sites; as a result, they exhibit outstanding catalytic activity in artificial photosynthesis: that is, CO2 photoreduction with H2O as the electron donor. Among them, TCOF-MnMo6 achieved the highest CO yield (37.25 µmol g-1 h-1 with ca. 100% selectivity) in a gas-solid reaction system. Furthermore, a mechanism study based on density functional theory (DFT) calculations demonstrated that the photoinduced electron transfer (PET) process occurs from the COF to the POM, and then CO2 reduction and H2O oxidation occur on the POM and COF, respectively. This work developed a method for a uniform dispersion of POM single clusters into a COF, which also shows the potential of using COF-POM functional materials in the field of photocatalysis.

Covalent-Bonding Oxidation Group and Titanium Cluster to Synthesize a Porous Crystalline Catalyst for Selective Photo-Oxidation Biomass Valorization.

The selective photo-oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) is important due to its substitute-role in polyester-fabrication. Here, a titanium-cluster based metal-covalent organic framework nanosheet has been synthesized through the covalent-coupling between Ti6 -NH2 and benzotrithiophene tricarbaldehyde (BTT). The integration of them endows the nanosheet with a visible-light-adsorption region, effective electron-hole separation-efficiency and suitable photo-oxidation ability. Specifically, its photo-selectivity for HMF-to-FDCA can be >95 % with ≈100 % conversion, which is more than 2, 5, and 10 times higher than MOF-901 (43 %), Ti6 -NH2 (19 %) and under-darkness (9 %), respectively. Notably, an O2 -based mechanism is proposed and the vital roles of Ti6 -NH2 and BTT are verified by DFT calculations. This work might facilitate the exploration of porous-crystalline-catalysts for selective biomass-valorization.

Stable Dioxin-Linked Metallophthalocyanine Covalent Organic Frameworks (COFs) as Photo-Coupled Electrocatalysts for CO2 Reduction.

In this work, we rationally designed a series of crystalline and stable dioxin-linked metallophthalocyanine covalent organic frameworks (COFs; MPc-TFPN COF, M=Ni, Co, Zn) under the guidance of reticular chemistry. As a novel single-site catalysts (SSCs), NiPc/CoPc-TFPN COF exhibited outstanding activity and selectivity for electrocatalytic CO2 reduction (ECR; Faradaic efficiency of CO (FECO )=99.8(±1.24) %/ 96.1(±1.25) % for NiPc/CoPc-TFPN COF). More importantly, when coupled with light, the FECO and current density (jCO ) were further improved across the applied potential range (-0.6 to -1.2 V vs. RHE) compared to the dark environment for NiPc-TFPN COF (jCO increased from 14.1 to 17.5 A g-1 at -0.9 V; FECO reached up to ca. 100 % at -0.8 to -0.9 V). Furthermore, an in-depth mechanism study was established by density functional theory (DFT) simulation and experimental characterization. For the first time, this work explored the application of COFs as photo-coupled electrocatalysts to improve ECR efficiency, which showed the potential of using light-sensitive COFs in the field of electrocatalysis.

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 , Bi2 WO6 , and α-Fe2 O3 ) 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 H2 O 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 H2 O oxidation, thus mimicking natural photosynthesis.

Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4.

The electrochemical CO2 reduction to high-value-added chemicals is one of the most promising and challenging research in the energy conversion field. An efficient ECR catalyst based on a Cu-based conductive metal-organic framework (Cu-DBC) is dedicated to producing CH4 with superior activity and selectivity, showing a Faradaic efficiency of CH4 as high as ~80% and a large current density of -203 mA cm-2 at -0.9 V vs. RHE. The further investigation based on theoretical calculations and experimental results indicates the Cu-DBC with oxygen-coordinated Cu sites exhibits higher selectivity and activity over the other two crystalline ECR catalysts with nitrogen-coordinated Cu sites due to the lower energy barriers of Cu-O4 sites during ECR process. This work unravels the strong dependence of ECR selectivity on the Cu site coordination environment in crystalline porous catalysts, and provides a platform for constructing highly selective ECR catalysts.

Controllable Synthesis of COFs-Based Multicomponent Nanocomposites from Core-Shell to Yolk-Shell and Hollow-Sphere Structure for Artificial Photosynthesis.

The precise tuning and multi-dimensional processing of covalent organic frameworks (COFs)-based materials into multicomponent superstructures with appropriate diversity are essential to maximize their advantages in catalytic reactions. However, up to now, it remains an ongoing challenge for the precise design of COFs-based multicomponent nanocomposites with diverse architectures. Herein, a metal organic framework (MOF)-sacrificed in situ acid-etching (MSISAE) strategy that enables continuous synthesis of core-shell, yolk-shell, and hollow-sphere COFs-based nanocomposites through tuning of core decomposition (NH2 -MIL-125 into TiO2 ) rate is developed. More importantly, due to the multiple active sites, fast transfer of carriers, increased light utilization ability, et al, one of the obtained samples, NH2 -MIL-125/TiO2 @COF-366-Ni-OH-HAc (yolk-shell) with special three components, exhibits high photocatalytic CO2 -to-CO conversion efficiency in the gas-solid mode. The MSISAE strategy developed in this work achieves the precise morphology design and control of multicomponent hybrid composites based on COFs, which may pave a new way in devealoping porous crystalline materials with powerful superstructures for multifunctional catalytic reactions.

Efficient Charge Migration in Chemically-Bonded Prussian Blue Analogue/CdS with Beaded Structure for Photocatalytic H2 Evolution.

The design of a powerful heterojunction structure and the study of the interfacial charge migration pathway at the atomic level are essential to mitigate the photocorrosion and recombination of electron-hole pairs of CdS in photocatalytic hydrogen evolution (PHE). A temperature-induced self-assembly strategy has been proposed for the syntheses of Prussian blue analogue (PBA)/CdS nanocomposites with beaded structure. The specially designed structure had evenly exposed CdS which can efficiently harvest visible light and inhibit photocorrosion; meanwhile, PBA with a large cavity provided channels for mass transfer and photocatalytic reaction centers. Remarkably, PB-Co/CdS-LT-3 exhibits a PHE rate of 57 228 µmol h-1 g-1, far exceeding that of CdS or PB-Co and comparable to those of most reported crystalline porous material-based photocatalysts. The high performances are associated with efficient charge migration from CdS to PB-Co through CN-Cd electron bridges, as revealed by the DFT calculations. This work sheds light on the exploration of heterostructure materials in efficient PHE.