Thiophene Sulfone Research Articles

Symmetry‐breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution

AbstractThe current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high‐performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry‐breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT‐1SO. The asymmetric structure of BBTT‐1SO proved beneficial for increasing multiple moment and polarizability. BBTT‐1SO‐containing polymers showed higher efficiencies for hydrogen evolution than their DBS‐containing counterparts by up to 166 %. PBBTT‐1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g−1 h−1 and an apparent quantum yield of 27.5 % at 500 nm. Transient spectroscopic studies indicated that the BBTT‐1SO‐based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT‐1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water‐PBBTT‐1SO polymer interactions in salt‐containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high‐performance photocatalysts for hydrogen evolution.

Symmetry-breaking of Dibenzo[b,d]thiophene Sulfone Enhancing Polaron Generation for Boosted Photocatalytic Hydrogen Evolution.

The current bottleneck in the development of efficient photocatalysts for hydrogen evolution is the limited availability of high-performance acceptor units. Over the past nine years, dibenzo[b,d]thiophene sulfone (DBS) has been the preferred choice for the acceptor unit. Despite extensive exploration of alternative structures as potential replacements for DBS, a superior substitute remains elusive. In this study, a symmetry-breaking strategy was employed on DBS to develop a novel acceptor unit, BBTT-1SO. The asymmetric structure of BBTT-1SO proved beneficial for increasing multiple moment and polarizability. BBTT-1SO-containing polymers showed higher efficiencies for hydrogen evolution than their DBS-containing counterparts by up to 166 %. PBBTT-1SO exhibited an excellent hydrogen evolution rate (HER) of 222.03 mmol g-1 h-1 and an apparent quantum yield of 27.5 % at 500 nm. Transient spectroscopic studies indicated that the BBTT-1SO-based polymers facilitated electron polaron formation, which explains their superior HERs. PBBTT-1SO also showed 14 % higher HER in natural seawater splitting than that in deionized water splitting. Molecular dynamics simulations highlighted the enhanced water-PBBTT-1SO polymer interactions in salt-containing solutions. This study presents a pioneering example of a substitute acceptor unit for DBS in the construction of high-performance photocatalysts for hydrogen evolution.

Conjugated Polymer/Recombinant Escherichia coli Biohybrid Systems for Photobiocatalytic Hydrogen Production.

Biohybrid photocatalysts are composite materials that combine the efficient light-absorbing properties of synthetic materials with the highly evolved metabolic pathways and self-repair mechanisms of biological systems. Here, we show the potential of conjugated polymers as photosensitizers in biohybrid systems by combining a series of polymer nanoparticles with engineered Escherichia coli cells. Under simulated solar light irradiation, the biohybrid system consisting of fluorene/dibenzo [b,d]thiophene sulfone copolymer (LP41) and recombinant E. coli (i.e., a LP41/HydA BL21 biohybrid) shows a sacrificial hydrogen evolution rate of 3.442 mmol g-1 h-1 (normalized to polymer amount). It is over 30 times higher than the polymer photocatalyst alone (0.105 mmol g-1 h-1), while no detectable hydrogen was generated from the E. coli cells alone, demonstrating the strong synergy between the polymer nanoparticles and bacterial cells. The differences in the physical interactions between synthetic materials and microorganisms, as well as redox energy level alignment, elucidate the trends in photochemical activity. Our results suggest that organic semiconductors may offer advantages, such as solution processability, low toxicity, and more tunable surface interactions with the biological components over inorganic materials.

Polymer Photocatalysts with Side Chain Induced Planarity for Increased Activity for Sacrificial Hydrogen Production from Water

AbstractConjugated polymers are promising materials for photocatalytic hydrogen evolution. However, most reported materials are not solution‐processible, limiting their potential for large‐scale application, for example as solution cast films. Flexible side‐chains are commonly introduced to provide solubility, but these often impart unfavorable properties, such as hydrophobicity, which lowers photocatalytic activity. Here, computational predictions are employed to aid in the design of chloroform soluble polymer photocatalysts that show increased planarity through favorable intramolecular interactions. Using this approach, three conjugated polymer photocatalysts with identical poly(benzene‐dibenzo[b,d]thiophene sulfone) backbones but different solubilizing side‐chains on the benzene‐ring are explored, i.e., tri(ethylene glycol), n‐decyloxy, and n‐dodecyl. These side‐chain variations significantly alterr the properties of the polymers, specifically energy levels, optical gap, and wettability. The hydrophobic n‐decyloxy functionalized polymer has a sacrificial hydrogen evolution rate of 17.0 µmol h−1 in suspension, while the hydrophilic tri(ethylene glycol) functionalized polymer is almost three times more active (45.4 µmol h−1). Conversely, no hydrogen evolution is observed for the purely alkyl side‐chain (n‐dodecyl) containing polymer due to the side‐chain induced torsion of the backbone. A thin‐film of the most active polymer exhibits a promising area‐normalized sacrificial hydrogen evolution rate of 7.4 ± 0.3 mmol h−1 m−2 under visible light irradiation.

Visible-light-responsive hybrid photocatalysts for quantitative conversion of CO2 to highly concentrated formate solutions.

Photocatalysts can use visible light to convert CO2 into useful products. However, to date photocatalysts for CO2 conversion are limited by insufficient long-term stability and low CO2 conversion rates. Here we report hybrid photocatalysts consisting of conjugated polymers and a ruthenium(ii)-ruthenium(ii) supramolecular photocatalyst which overcome these challenges. The use of conjugated polymers allows for easy fine-tuning of structural and optoelectronic properties through the choice of monomers, and after loading with silver nanoparticles and the ruthenium-based binuclear metal complex, the resulting hybrid systems displayed remarkably enhanced activity for visible light-driven CO2 conversion to formate. In particular, the hybrid photocatalyst system based on poly(dibenzo[b,d]thiophene sulfone) drove the very active, durable and selective photocatalytic CO2 conversion to formate under visible light irradiation. The turnover number was found to be very high (TON = 349 000) with a similarly high turnover frequency (TOF) of 6.5 s-1, exceeding the CO2 fixation activity of ribulose-1,5-bisphosphate carboxylase/oxygenase in natural photosynthesis (TOF = 3.3 s-1), and an apparent quantum yield of 11.2% at 440 nm. Remarkably, quantitative conversion of CO2 (737 μmol, 16.5 mL) to formate was achieved using only 8 mg of the hybrid photocatalyst containing 80 nmol of the supramolecular photocatalyst at standard temperature and pressure. The system sustained photocatalytic activity even after further replenishment of CO2, yielding a very high concentration of formate in the reaction solution up to 0.40 M without significant photocatalyst degradation within the timeframe studied. A range of experiments together with density functional theory calculations allowed us to understand the activity in more detail.

Films of linear conjugated polymer as photoanodes for oxidation reactions.

Photoelectrochemical (PEC) devices hold huge potential to convert solar energy into chemical energy. However, the high cost of raw materials and film processing has hindered its practical use. In this study, we attempt to tackle this issue by fabricating straightforward semiconducting polymer films. These films function as photoanodes for various oxidation reactions, including water oxidation and oxidative organosynthesis. The structures of the polymer were assessed by incorporating electron-rich and electron-deficient co-monomers into dibenzo[b,d]thiophene sulfone materials. Furthermore, to gain comprehensive insight into the performance, we conducted both steady-state and in operando investigations, revealing that the active site on the polymer surface determines the rate of the conversion process. This study marks a significant stride towards leveraging economically viable semiconductors in PEC systems for efficient solar-to-chemical conversions. It addresses the challenges of high material costs and complex film processing, paving the way for the scaled-up application of this burgeoning technology.

Why Do Sulfone-Containing Polymer Photocatalysts Work So Well for Sacrificial Hydrogen Evolution from Water?

Many of the highest-performing polymer photocatalysts for sacrificial hydrogen evolution from water have contained dibenzo[b,d]thiophene sulfone units in their polymer backbones. However, the reasons behind the dominance of this building block are not well understood. We study films, dispersions, and solutions of a new set of solution-processable materials, where the sulfone content is systematically controlled, to understand how the sulfone unit affects the three key processes involved in photocatalytic hydrogen generation in this system: light absorption; transfer of the photogenerated hole to the hole scavenger triethylamine (TEA); and transfer of the photogenerated electron to the palladium metal co-catalyst that remains in the polymer from synthesis. Transient absorption spectroscopy and electrochemical measurements, combined with molecular dynamics and density functional theory simulations, show that the sulfone unit has two primary effects. On the picosecond timescale, it dictates the thermodynamics of hole transfer out of the polymer. The sulfone unit attracts water molecules such that the average permittivity experienced by the solvated polymer is increased. We show that TEA oxidation is only thermodynamically favorable above a certain permittivity threshold. On the microsecond timescale, we present experimental evidence that the sulfone unit acts as the electron transfer site out of the polymer, with the kinetics of electron extraction to palladium dictated by the ratio of photogenerated electrons to the number of sulfone units. For the highest-performing, sulfone-rich material, hydrogen evolution seems to be limited by the photogeneration rate of electrons rather than their extraction from the polymer.

Tuning Acceptor Length in Photocatalytic Donor‐Acceptor Conjugated Polymers for Efficient Solar‐to‐Hydrogen Energy Conversion

Comprehensive SummaryThe development of conjugated polymer photocatalysts for efficient solar‐to‐hydrogen energy conversion is highly desirable for the sustainability of our society. Although the construction of donor‐acceptor (D‐A) structure in conjugated polymer photocatalysts for solar‐to‐hydrogen energy conversion has been well documented, less attention has been paid on how large D and how large A units combined together could achieve the best performance. Herein, a series of D‐A copolymers P(BDT‐DBTSOx) (x = 7, 19, 39, and 79) composed of a benzodithiophene (BDT) donor unit and an oligomeric dibenzo[b,d]thiophene sulfone (DBTSO) acceptor segment were synthesized and studied. It was found that the polymer photocatalytic stabilities under full‐arc irradiation improved upon shortening the length of the acceptor segment. Under visible light irradiation and in the presence of 3 wt% Pt cocatalyst, P(BDT‐DBTSO79) displayed the best performance with an optimal hydrogen evolution rate of 119.3 ± 5.8 mmol·g–1·h–1. This is 1.4‐fold as that of DBTSO homopolymer and 22.5‐fold as that of BDT/DBTSO alternative copolymer, highlighting the importance of acceptor length in D‐A structure for achieving high photocatalytic performance.

The introduction of dual pyridinic N atoms into dibenzo[b,d]thiophene sulfone containing conjugated polymers for improved hydrogen evolution: Experimental and theoretical study

Research a new type of semiconductor photocatalyst and apply it to photocatalytic water splitting to produce hydrogen. This is the most important topic in today's society. Therefore, we report four linear organic polymers PH-1, PH-2, PN-1 and PN-2, which are formed by the condensation of dibenzothiophene-S, S-dioxide units with a series of derivatives of benzene respectively and used for photocatalytic hydrogen evolution. What’s more, we also conducted a series of detailed characterization experiments on the four polymers, such as UV–vis, XPS, XRD, etc., to explore their molecular structure and optical properties. Compared with the polymer PH-1 and PH-2, the polymer PN-1 and PN-2 containing nitrogen element can better adjust the structure, reduce the band gap value, increase the specific surface area, and accelerate the separation of electrons and holes, PN-2 had the highest hydrogen evolution rate of 6658 μmol g−1 h−1 among four polymers without Pt as the co-catalyst under full arc irradiation. This work not only synthesized the four photocatalysts, but also opened up a new way for the conversion of solar energy into chemical fuels.

Copper-Catalyzed Umpolung of N-2,2,2-Trifluoroethylisatin Ketimines for the Enantioselective 1,3-Dipolar Cycloaddition with Benzo[b]thiophene Sulfones.

A copper-catalyzed umpolung of N-2,2,2-trifluoroethylisatin ketimines for the enantioselective 1,3-dipolar cycloaddition with benzo[b]thiophene sulfones was developed. Using a catalyst system consisting of an (S,Sp)-tBu-Phosferrox ligand, Cu(OTf)2, and Cs2CO3, a range of pentacyclic spirooxindoles containing pyrrolidine and benzo[b]sulfolane subunits were obtained in high efficiency with excellent regio-, diastereo-, and enantioselectivites under mild conditions. The practicality and versatility of the reaction were also demonstrated.

Photocatalytic Overall Water Splitting Under Visible Light Enabled by a Particulate Conjugated Polymer Loaded with Palladium and Iridium**

AbstractPolymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large‐scale hydrogen energy production. Here we show that the palladium/iridium oxide‐loaded homopolymer of dibenzo[b,d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co‐catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co‐catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co‐catalyst.

Photocatalytic Overall Water Splitting Under Visible Light Enabled by a Particulate Conjugated Polymer Loaded with Palladium and Iridium.

Polymer photocatalysts have received growing attention in recent years for photocatalytic hydrogen production from water. Most studies report hydrogen production with sacrificial electron donors, which is unsuitable for large‐scale hydrogen energy production. Here we show that the palladium/iridium oxide‐loaded homopolymer of dibenzo[b,d]thiophene sulfone (P10) facilitates overall water splitting to produce stoichiometric amounts of H2 and O2 for an extended period (>60 hours) after the system stabilized. These results demonstrate that conjugated polymers can act as single component photocatalytic systems for overall water splitting when loaded with suitable co‐catalysts, albeit currently with low activities. Transient spectroscopy shows that the IrO2 co‐catalyst plays an important role in the generation of the charge separated state required for water splitting, with evidence for fast hole transfer to the co‐catalyst.

Linear conjugated polymer photocatalysts with various linker units for photocatalytic hydrogen evolution from water.

Polymer photocatalysts have shown potential for light-driven hydrogen evolution from water. Here we studied the relative importance of the linker type in two series of conjugated polymers based on dibenzo[b,d]thiophene sulfone and dimethyl-9H-fluorene. The alkenyl-linked polymers were found to be more active photocatalysts than their alkyl and alkyne-linked counterparts. The co-polymer of dibenzo[b,d]thiophene sulfone and 1,2-diphenylethene has a hydrogen evolution rate of 3334 μmol g-1 h-1 and an external quantum efficiency of 5.6% at 420 nm.

Time-Resolved Raman Spectroscopy of Polaron Formation in a Polymer Photocatalyst

Polymer photocatalysts are a synthetically diverse class of materials that can be used for the production of solar fuels such as H2, but the underlying mechanisms by which they operate are poorly understood. Time-resolved vibrational spectroscopy provides a powerful structure-specific probe of photogenerated species. Here we report the use of time-resolved resonance Raman (TR3) spectroscopy to study the formation of polaron pairs and electron polarons in one of the most active linear polymer photocatalysts for H2 production, poly(dibenzo[b,d]thiophene sulfone), P10. We identify that polaron-pair formation prior to thermalization of the initially generated excited states is an important pathway for the generation of long-lived photoelectrons.

Coal desulfurization by photocatalytic oxidation in the presence of [HO2MMim][HSO4] and H2O2

Photocatalytic oxidation has been widely used in sulfur oxidation due to its mild reaction conditions. In order to improve the efficiency of removing sulfur from coal, especially the organic sulfur, TiO2, SiO2 and modified SiO2 were used as photocatalysts under UV lamp irradiation in the presence of 1-carboxymethyl-3-methylimidazole bisulfite ([HO2MMim][HSO4]) and hydrogen peroxide (H2O2). The results show that the photocatalysts played important roles in coal desulfurization. The desulfurization rate of [HO2MMim][HSO4]–H2O2 (1:10) treatment on coal was only 16.89%, while after adding TiO2, e.g. [HO2MMim][HSO4]–H2O2-TiO2 (1:10:4), it increases to 38.46% and the removing rate of organic sulfur approached 20.17% under normal temperature and pressure on a basis of photocatalysis. According to FTIR and XPS measurements, it is found that the catalytic oxidation can be accelerated in the presence of photocatalysts under ultraviolet irradiation, and the thiophene conversion can be enhanced significantly. Generally, TiO2 is more efficient in organic sulfur removal than SiO2 during photocatalytic oxidation. The results of quantum chemistry calculation indicates that thiophene sulfone could be produced much easier than the thiophene ring-cleaved reaction when thiophene was oxidized in the presence of hydroxyl radicals. In addition, compared to the traditional methods, the photocatalytic desulfurization only show a slight reduction of combustion heat value according to TG-DSC-DDSC measurements.

Tracking Charge Transfer to Residual Metal Clusters in Conjugated Polymers for Photocatalytic Hydrogen Evolution

Semiconducting polymers are versatile materials for solar energy conversion and have gained popularity as photocatalysts for sunlight-driven hydrogen production. Organic polymers often contain residual metal impurities such as palladium (Pd) clusters that are formed during the polymerization reaction, and there is increasing evidence for a catalytic role of such metal clusters in polymer photocatalysts. Using transient and operando optical spectroscopy on nanoparticles of F8BT, P3HT, and the dibenzo[b,d]thiophene sulfone homopolymer P10, we demonstrate how differences in the time scale of electron transfer to Pd clusters translate into hydrogen evolution activity optima at different residual Pd concentrations. For F8BT nanoparticles with common Pd concentrations of >1000 ppm (>0.1 wt %), we find that residual Pd clusters quench photogenerated excitons via energy and electron transfer on the femto-nanosecond time scale, thus outcompeting reductive quenching. We spectroscopically identify reduced Pd clusters in our F8BT nanoparticles from the microsecond time scale onward and show that the predominant location of long-lived electrons gradually shifts to the F8BT polymer when the Pd content is lowered. While a low yield of long-lived electrons limits the hydrogen evolution activity of F8BT, P10 exhibits a substantially higher hydrogen evolution activity, which we demonstrate results from higher yields of long-lived electrons due to more efficient reductive quenching. Surprisingly, and despite the higher performance of P10, long-lived electrons reside on the P10 polymer rather than on the Pd clusters in P10 particles, even at very high Pd concentrations of 27000 ppm (2.7 wt %). In contrast, long-lived electrons in F8BT already reside on Pd clusters before the typical time scale of hydrogen evolution. This comparison shows that P10 exhibits efficient reductive quenching but slow electron transfer to residual Pd clusters, whereas the opposite is the case for F8BT. These findings suggest that the development of even more efficient polymer photocatalysts must target materials that combine both rapid reductive quenching and rapid charge transfer to a metal-based cocatalyst.

Theoretical study on the desulfurization mechanisms of thiophene and benzothiophene under inert and oxidative atmospheres

A detailed theoretical study of desulfurization mechanisms of thiophene and benzo thiophene was performed under inert and oxidative atmospheres. Density functional theory (DFT) was used to investigate the 13 reaction pathways of their desulfurization mechanisms under these two atmospheres. The feasibility of each reaction was analyzed thermodynamically and kinetically. The calculated results show that it is thermodynamically and kinetically unfavorable for thiophenes to desulfurize under inert atmosphere, if a H2 directly attacks their S atoms and C-S bonds. This is resulted by their extremely high energy barriers and high reaction energies. However, the desulfurization mechanisms of thiophenes may be thermodynamically dominated by Diels-Alder reaction under inert atmosphere. Compared with inert atmosphere, it is much easier for thiophenes to desulfurize under oxidative atmosphere. The reason is that C-S bond strength of thiophenes-OH and sulfones is much lower than that of thiophenes based on Mayer bond order (MBO) analysis. It is found that thiophenes oxidation desulfurization is very possibly initiated by oxidative agent OH rather than thiophenes C-S bond directly attacked by O2. In addition, Diels-Alder reaction between thiophene sulfones can also possess very low barrier reaction pathways.

Organocatalytic enantioselective tandem sulfa-Michael/aldol reaction to access dihydrothiopyran-fused benzosulfolane skeletons bearing three contiguous stereocenters.

The first organocatalytic diastereo- and enantioselective tandem sulfa-Michael/aldol reaction of 2-mercaptoindole-3-carbaldehydes and 2-mercaptobenzaldehydes with benzo[b]thiophene sulfones was developed. With multiple hydrogen-bonding thiourea as a catalyst, a wide range of polycyclic dihydrothiopyran-fused benzosulfolanes were smoothly obtained with excellent results (up to 99% yield, >20 : 1 dr and 99% ee) under mild reaction conditions.

1,3,5-Triazine and dibenzo[b,d]thiophene sulfone based conjugated porous polymers for highly efficient photocatalytic hydrogen evolution.

Organic conjugated porous polymers, triazine-Ph-CPP and triazine-Th-CPP, are synthesized and characterized. Without further addition of co-catalysts, triazine-Ph-CPP exhibits a HER of 16 287 μmol g-1 h-1 and an apparent quantum yield of 61.5% at 365 nm, which demonstrates that the dibenzo[b,d]thiophene sulfone and 1,3,5-triazine based polymer is a unique prototype of a highly efficient hydrogen evolution photocatalyst.

Structure–activity relationships in well-defined conjugated oligomer photocatalysts for hydrogen production from water

Oligomer chain length and backbone twisting were found to have a strong effect on optoelectronic properties but a trimer of dibenzo[b,d]thiophene sulfone was found to have high photocatalytic activity approaching that of its polymer analogue.