A stable covalent organic framework for photocatalytic carbon dioxide reduction.
ABSTRACT: Photocatalytic conversion of CO2 into fuels is an important challenge for clean energy research and has attracted considerable interest. Here we show that tethering molecular catalysts-a rhenium complex, [Re(bpy)(CO)3Cl]-together in the form of a crystalline covalent organic framework (COF) affords a heterogeneous photocatalyst with a strong visible light absorption, a high CO2 binding affinity, and ultimately an improved catalytic performance over its homogeneous Re counterpart. The COF incorporates bipyridine sites, allowing for ligation of the Re complex, into a fully ?-conjugated backbone that is chemically robust and promotes light-harvesting. A maximum rate of 1040 ?mol g-1 h-1 for CO production with 81% selectivity was measured. CO production rates were further increased up to 1400 ?mol g-1 h-1, with an improved selectivity of 86%, when a photosensitizer was added. Addition of platinum resulted in production of syngas, hence, the co-formation of H2 and CO, the chemical composition of which could be adjusted by varying the ratio of COF to platinum. An amorphous analog of the COF showed significantly lower CO production rates, suggesting that crystallinity of the COF is beneficial to its photocatalytic performance in CO2 reduction.
Project description:Solar hydrogen (H2) evolution from water utilizing covalent organic frameworks (COFs) as heterogeneous photosensitizers has gathered significant momentum by virtue of the COFs' predictive structural design, long-range ordering, tunable porosity, and excellent light-harvesting ability. However, most photocatalytic systems involve rare and expensive platinum as the co-catalyst for water reduction, which appears to be the bottleneck in the development of economical and environmentally benign solar H2 production systems. Herein, we report a simple, efficient, and low-cost all-in-one photocatalytic H2 evolution system composed of a thiazolo[5,4-d]thiazole-linked COF (TpDTz) as the photoabsorber and an earth-abundant, noble-metal-free nickel-thiolate hexameric cluster co-catalyst assembled in situ in water, together with triethanolamine (TEoA) as the sacrificial electron donor. The high crystallinity, porosity, photochemical stability, and light absorption ability of the TpDTz COF enables excellent long-term H2 production over 70 h with a maximum rate of 941 μmol h-1 g-1, turnover number TONNi > 103, and total projected TONNi > 443 until complete catalyst depletion. The high H2 evolution rate and TON, coupled with long-term photocatalytic operation of this hybrid system in water, surpass those of many previously known organic dyes, carbon nitride, and COF-sensitized photocatalytic H2O reduction systems. Furthermore, we gather unique insights into the reaction mechanism, enabled by a specifically designed continuous-flow system for non-invasive, direct H2 production rate monitoring, providing higher accuracy in quantification compared to the existing batch measurement methods. Overall, the results presented here open the door toward the rational design of robust and efficient earth-abundant COF-molecular co-catalyst hybrid systems for sustainable solar H2 production in water.
Project description:BACKGROUND:Syngas fermentation, the bioconversion of CO, CO2, and H2 to biofuels and chemicals, has undergone considerable optimization for industrial applications. Even more, full-scale plants for ethanol production from syngas fermentation by pure cultures are being built worldwide. The composition of syngas depends on the feedstock gasified and the gasification conditions. However, it remains unclear how different syngas mixtures affect the metabolism of carboxidotrophs, including the ethanol/acetate ratios. In addition, the potential application of mixed cultures in syngas fermentation and their advantages over pure cultures have not been deeply explored. In this work, the effects of CO2 and H2 on the CO metabolism by pure and mixed cultures were studied and compared. For this, a CO-enriched mixed culture and two isolated carboxidotrophs were grown with different combinations of syngas components (CO, CO:H2, CO:CO2, or CO:CO2:H2). RESULTS:The CO metabolism of the mixed culture was somehow affected by the addition of CO2 and/or H2, but the pure cultures were more sensitive to changes in gas composition than the mixed culture. CO2 inhibited CO oxidation by the Pleomorphomonas-like isolate and decreased the ethanol/acetate ratio by the Acetobacterium-like isolate. H2 did not inhibit ethanol or H2 production by the Acetobacterium and Pleomorphomonas isolates, respectively, but decreased their CO consumption rates. As part of the mixed culture, these isolates, together with other microorganisms, consumed H2 and CO2 (along with CO) for all conditions tested and at similar CO consumption rates (2.6 ± 0.6 mmol CO L-1 day-1), while maintaining overall function (acetate production). Providing a continuous supply of CO by membrane diffusion caused the mixed culture to switch from acetate to ethanol production, presumably due to the increased supply of electron donor. In parallel with this change in metabolic function, the structure of the microbial community became dominated by Geosporobacter phylotypes, instead of Acetobacterium and Pleomorphomonas phylotypes. CONCLUSIONS:These results provide evidence for the potential of mixed-culture syngas fermentation, since the CO-enriched mixed culture showed high functional redundancy, was resilient to changes in syngas composition, and was capable of producing acetate or ethanol as main products of CO metabolism.
Project description:We developed new cyclic Re(i)-based trinuclear redox photosensitizers with both high oxidation power in the excited state and strong reduction power in the reduced form. These excellent properties were achieved by introducing electron-donating groups on the diimine ligand of the Re(i) metal centre and by connecting each Re(i) unit with polyphenyl-bisphosphine bridging ligands. These Re-rings were applied to homogenous visible light-driven photocatalytic CO2 reduction in conjunction with various mononuclear catalysts, such as Re(i), Ru(ii) and Mn(i) metal complexes, employing a relatively weak sacrificial electron donor, triethanolamine. Each system showed good product selectivity (CO or HCOOH) and an excellent quantum yield of product formation ?CO = 0.60 to 0.74 using fac-[ReI(bpy)(CO)3(CH3CN)]+, ?HCOOH = 0.58 using trans(Cl)-RuII(dtbb)(CO)2Cl2 and ?HCOOH = 0.48 using a fac-[MnI(dtbb)(CO)3(CH3CN)]+ catalyst. The high photocatalytic efficiencies for CO2 reduction are attributed to efficient reductive quenching of the Re-ring by triethanolamine and fast electron transfer from the generated one-electron-reduced species of the ring to the catalyst.
Project description:Syngas, a CO and H2 mixture mostly generated from non-renewable fossil fuels, is an essential feedstock for production of liquid fuels. Electrochemical reduction of CO2 and H+/H2O is an alternative renewable route to produce syngas. Here we introduce the concept of coupling a hydrogen evolution reaction (HER) catalyst with a CDots/C3N4 composite (a CO2 reduction catalyst) to achieve a cheap, stable, selective and efficient route for tunable syngas production. Co3O4, MoS2, Au and Pt serve as the HER component. The Co3O4-CDots-C3N4 electrocatalyst is found to be the most efficient among the combinations studied. The H2/CO ratio of the produced syngas is tunable from 0.07:1 to 4:1 by controlling the potential. This catalyst is highly stable for syngas generation (over 100?h) with no other products besides CO and H2. Insight into the mechanisms balancing between CO2 reduction and H2 evolution when applying the HER-CDots-C3N4 catalyst concept is provided.
Project description:The activity and selectivity of simple photocatalysts for CO2 reduction remain limited by the insufficient photophysics of the catalysts, as well as the low solubility and slow mass transport of gas molecules in/through aqueous solution. In this study, these limitations are overcome by constructing a triphasic photocatalytic system, in which polymeric carbon nitride (CN) is immobilized onto a hydrophobic substrate, and the photocatalytic reduction reaction occurs at a gas-liquid-solid (CO2 -water-catalyst) triple interface. CN anchored onto the surface of a hydrophobic substrate exhibits an approximately 7.2-fold enhancement in total CO2 conversion, with a rate of 415.50??mol?m-2 ?h-1 under simulated solar light irradiation. This value corresponds to an overall photosynthetic efficiency for full water-CO2 conversion of 0.33?%, which is very close to biological systems. A remarkable enhancement of direct C2 hydrocarbon production and a high CO2 conversion selectivity of 97.7?% are observed. Going from water oxidation to phosphate oxidation, the quantum yield is increased to 1.28?%.
Project description:We demonstrate photocatalytic hydrogen evolution using COF photosensitizers with molecular proton reduction catalysts for the first time. With azine-linked N2-COF photosensitizer, chloro(pyridine)cobaloxime co-catalyst, and TEOA donor, H<sub>2</sub> evolution rate of 782 ?mol h<sup>-1</sup> g<sup>-1</sup> and TON of 54.4 has been obtained in a water/acetonitrile mixture. PXRD, solid-state spectroscopy, EM analysis, and quantum-chemical calculations suggest an outer sphere electron transfer from the COF to the co-catalyst which subsequently follows a monometallic pathway of H<sub>2</sub> generation from the Co<sup>III</sup>-hydride and/or Co<sup>II</sup>-hydride species.
Project description:Photocatalytic CO<sub>2</sub> reduction represents a sustainable route to generate syngas (the mixture of CO and H<sub>2</sub>), which is a key feedstock to produce liquid fuels in industry. Yet this reaction typically suffers from two limitations: unsuitable CO/H<sub>2</sub> ratio and serious charge recombination. This paper describes the production of syngas from photocatalytic CO<sub>2</sub> reduction with a tunable CO/H<sub>2</sub> ratio <i>via</i> adjustment of the components and surface structure of CuPt alloys and construction of a TiO<sub>2</sub> mesoporous hollow sphere with spatially separated cocatalysts to promote charge separation. Unlike previously reported cocatalyst-separated hollow structures, we firstly create a reductive outer surface that is suitable for the CO<sub>2</sub> reduction reaction. A high evolution rate of 84.2 ?mol h<sup>-1</sup> g<sup>-1</sup> for CO and a desirable CO/H<sub>2</sub> ratio of 1?:?2 are achieved. The overall solar energy conversion yield is 0.108%, which is higher than those of traditional oxide and sulfide based catalysts (generally about 0.006-0.042%). Finally, density functional theory calculations and kinetic experiments by replacing H<sub>2</sub>O with D<sub>2</sub>O reveal that the enhanced activity is mainly determined by the reduction energy of CO* and can be affected by the stability of COOH*.
Project description:Synthesizing H<sub>2</sub> O<sub>2</sub> from water and air via a photocatalytic approach is ideal for efficient production of this chemical at small-scale. However, the poor activity and selectivity of the 2 e<sup>-</sup> water oxidation reaction (WOR) greatly restricts the efficiency of photocatalytic H<sub>2</sub> O<sub>2</sub> production. Herein we prepare a bipyridine-based covalent organic framework photocatalyst (denoted as COF-TfpBpy) for H<sub>2</sub> O<sub>2</sub> production from water and air. The solar-to-chemical conversion (SCC) efficiency at 298 K and 333 K is 0.57 % and 1.08 %, respectively, which are higher than the current reported highest value. The resulting H<sub>2</sub> O<sub>2</sub> solution is capable of degrading pollutants. A mechanistic study revealed that the excellent photocatalytic activity of COF-TfpBpy is due to the protonation of bipyridine monomer, which promotes the rate-determining reaction (2 e<sup>-</sup> WOR) and then enhances Yeager-type oxygen adsorption to accelerate 2 e<sup>-</sup> one-step oxygen reduction. This work demonstrates, for the first time, the COF-catalyzed photosynthesis of H<sub>2</sub> O<sub>2</sub> from water and air; and paves the way for wastewater treatment using photocatalytic H<sub>2</sub> O<sub>2</sub> solution.
Project description:The inertness of the C-H bond in CH4 poses significant challenges to selective CH4 oxidation, which often proceeds all the way to CO2 once activated. Selective oxidation of CH4 to high-value industrial chemicals such as CO or CH3OH remains a challenge. Presently, the main methods to activate CH4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH4 oxidation exhibit limited control over the product selectivity, with CO2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO2 grown by atomic layer deposition (ALD), which features high concentrations of Ti3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO2. Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO2 reduction mechanisms. Our results not only present a new route to selective CH4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.
Project description:In the photoreduction of CO2 to CO, the competitive H2 evolution is always inevitable due to the approximate reduction potentials of H+/H2 and CO2/CO, which results in poor selectivity for CO production. Herein, imidazolium-type ionic liquid- (IL-) modified rhenium bipyridine-based porous organometallic polymers (Re-POMP-IL) were designed as efficient and selective photocatalysts for visible-light CO2 photoreduction to CO based on the affinity of IL with CO2. Photoreduction studies demonstrated that CO2 photoreduction promoted by Re-POMP-IL functioning as the catalyst exhibits excellent CO selectivity up to 95.5% and generate 40.1?mmol CO/g of Re-POMP-IL1.0 (obtained by providing equivalent [(5,5'-divinyl-2,2'-bipyridine)Re(CO)3Cl] and 3-ethyl-1-vinyl-1H-imidazol-3-ium bromide) at 12?h, outperforming that attained with the corresponding Re-POMP analogue without IL, which highlights the crucial role of IL. Notably, CO2 adsorption, light harvesting, and transfer of photogenerated charges as key steps for CO2RR were studied by employing POMPs modified with different amounts of IL as photocatalysts, among which the CO2 affinity as an important factor for POMPs catalyzed CO2 reduction is revealed. Overall, this work provides a practical pathway to improve the CO2 photoreduction efficiency and CO selectivity by employing IL as a regulator.