Because of their large surface area and persistent pores that have exceptional adsorption capabilities, porous organic/inorganic polymers (POIPs) with octavinylsilsesquioxane (OVS) units have attracted much interest recently. In this study aimed at removing Rhodamine B (RhB) from wastewater, we utilized OVS nanoparticles synthesized through the Heck coupling process to produce two distinct types: OVS-DBC-PO and OVS-DBC-BT POIPs. OVS and a variety of chemical compounds containing Br, such as tetrabromodibenzo[g,p]chrysene (DBC-Br4), 2,6-bis(4-bromophenyl)pyridine 1-oxide (PO-Br2), and 4,7-dibromobenzo[c][1,2,5]thiadiazole (BTBr2) were involved in the reactions. Thermogravimetric analysis (TGA) results revealed that the high thermal decomposition temperature (Td10) of OVS-DBC-PO and OVS-DBC-BT POIPs were 447 degrees C and 543 degrees C, respectively. Additionally, the OVS-POIPs demonstrated significant porosity, with the OVS-DBC-BT POIP exhibiting the highest specific BET surface area (SA BET ) of 386 m 2 g-1 . OVS-DBC-PO and OVS-DBC-BT POIPs exhibit excep- tional porosity character. Based on dye adsorption measurements, RhB interacts with functional groups on the OVS-POIP samples' surface and penetrates their pores, enhancing the number of contact sites and the effec- tiveness of adsorption. Both OVS-DBC-PO and OVS-DBC-BT POIPs demonstrated maximum adsorption capacities of 65 and 66 mg g-1 , respectively, at a pH of 4 and a temperature of 25 degrees C. As a result, OVS-DBC-PO and OVS- DBC-BT POIP materials could be viewed as efficient absorbents for removing RhB from aqueous solutions and this study presents a novel way of making POIPs, which are adsorbents used in the filtration and treatment of water.

Covalent organic frameworks (COFs), which have layered stacking structures, extended pi-conjugation, and periodic frameworks have become a promising class of materials for a wide range of applications. However, their synthetic pathways frequently need high temperatures, enclosed systems under high pressures, an inert atmosphere, and extended reaction time, which restrict their practicality in real-world applications. Herein, the use of gamma irradiation is presented to synthesize highly crystalline COFs at room temperature under an open-air condition within a short time. This is demonstrated that there is no significant difference in crystallinity of COFs by gamma irradiation under air, N2 or Ar atmosphere conditions. Moreover, this approach can successfully fabricate COFs in the vessel with different degrees of transparency or even in a plastic container. Importantly, this strategy is applicable not only to imine linkage of COFs but also effective to the imide linkages of COFs. Most importantly, these COFs demonstrate improved crystallinity, surface area, and thermal stability in comparison to the corresponding materials synthesized via the solvothermal method. Finally, a COF synthesized through gamma irradiation exhibits remarkable photocatalytic activity in promoting the sacrificial hydrogen evolution from water, displaying a more catalytic efficiency compared with that of its solvothermal analogue. The advancement of new forms of energy sources has been the focus of research to develop more green and high-throughput synthetic techniques. In this work, gamma irradiation is used as a promising approach under an open-air condition at room temperature within a short time for the synthesis of high crystalline COFs. image

Hydrogels show promise in preventing inorganic catalysis aggregation during hydrogen evolution. However, the incompatible intrinsic properties of inorganics and hydrogels can cause catalyst release during the reaction. One solution is incorporating polymer photocatalysts into hydrogels, but low photocatalytic efficiency due to anti-synergetic effects between polymers and hydrogels remains a challenge. Herein, we developed all-in-one photocatalytic microreactors (PMRs) with excellent stability and efficiency by strongly entangling polymers with hydrogels and designing heterogeneous hydrogels. This approach prevents catalyst loss while achieving a high hydrogen evolution efficiency, self-healability, and stretchability. Moreover, PMRs maintain their efficiency even after they undergo freeze-drying and rehydration. Remarkably, we demonstrate the construction of PMRs into three-dimensional (3D) structures via 3D-printing at room temperature without additional supporting material. In light of these advantages, we have demonstrated a strategy for rapidly manufacturing PMRs with high stability, reactivity, and 3D-printability, which has significant potential for practical applications.

In this study, we employed the Heck reaction method to synthesize three types of hybrid porous organic/inorganic polymers (HPPs) incorporating octavinylsilsesquioxane (OVS) units. Specifically, we synthesized OVS-TBNDBTH, OVS-TBN-THS, and OVS-TBN-THSO2 HPPs by reacting OVS with different brominated organic compounds, namely, 2,7,10,15-tetrabromodibenzo[g,p]chrysene (TBN-Br4)/2,8-dibromodibenzo[b,d]thiophene (DBTH-Br2), TBN-Br4/2,3,7,8-tetrabromothianthrene (THS-Br4), and TBN-Br4/2,3,7,8-tetrabromothianthrene-5,5,10,10-tetraoxide (THSO2-Br4). Based on thermal analysis (TGA), the onset decomposition temperatures (Td10) for these HPPs were as follows: OVS-TBN-DBTH at 575 degrees C, OVS-TBN-THS at 313 degrees C, and OVS-TBN-THSO2 at 490 degrees C. Additionally, these HPPs exhibited high char yields, with values of 83, 53, and 67 wt% for OVS-TBNDBTH, OVS-TBN-THS, and OVS-TBN-THSO2 HPPs, respectively. Furthermore, when analyzed using nitrogen adsorption-desorption measurements, both OVS-TBN-DBTH and OVS-TBN-THSO2 HPPs demonstrated impressive specific surface areas (SBET) of up to 380 m2/g. In addition, the OVS-TBN-DBTH and OVS-TBN-THSO2 HPPs provide an adsorption capacity of 70.62 and 77.1 mg g-1 (qmax from Langmuir isothermal Mode) toward RhB dyestuff at room temperature. In this adsorption system, after calculation, the OVS-TBN-THS HPP could be inferred that the adsorption is a pseudo-first order adsorption model. The OVS-TBN-THS HPP and OVS-TBNTHSO2 HPP in the pseudo-secondary order model have a better representation of the adsorption system for rhodamine B. This study introduces an innovative method for developing HPPs as adsorbents for water treatment and purification.

An organic synaptic transistor was fabricated with a covalent organic polymer MT-TP to mimic the behavior of biological synapses.

So far, achieving high apparent quantum yield (AQY) in polymeric photocatalysts at wavelengths up to 500 nm has never been achieved. Covalent organic polymers (COPs) have the advantage of high structure function tunability. However, despite decades of development, COPs still lag in achieving high AQY value, highlighting the need for an optimal COP structural design for efficient photocatalysis. Herein, we present a green synthetic approach to synthesize five hydrophilic and non-conjugated linkage with D-pi-A system benzoin-based COPs by self-condensation of multiformly monomers. Charge kinetic carrier and femtosecond transient absorption (fsTAS) demonstrate the efficient charge transport of benzoin-based COPs. Among the synthesized photocatalysts, B-PyTT-COP (D-pi-A) outperforms the COP family, with an excellent HER of 233.81 mu mol h-1 (77935 mu mol g- 1h- 1) using Platinum as co-catalyst. Remarkedly, B-PyTT-COP has achieved an exceptional ability to generate a high AQY value at 500 nm (65.35 %), surpassing all other materials examined thus far.

Organic‐conjugated polymer dots (Pdots) are emerging as promising photocatalysts for solar‐driven hydrogen production. However, organic solvents are commonly used as cosolvents in photocatalytic systems to promote the dispersion of organic materials and improve the overall efficiency of the photocatalytic process. Herein, two naphthalenediimide (NDI)‐based Pdots, with and without surfactant, are fabricated and presented as highly efficient and stable photocatalysts for visible‐light‐driven hydrogen generation in a solvent‐free organic system for the first time. The prepared Pdots exhibit high photocatalytic activity and remarkable photostability. Achieving high efficiency and long‐term photostability is essential for the future commercialization of large‐scale hydrogen production. Furthermore, the NDI‐BTF‐PS‐PEG‐COOH Pdots of the dual acceptor (A1‐D‐A2‐D system) consisting of a strong acceptor (NDI, A1) and a weak acceptor (BTF, A2) exhibit high photocatalytic efficiencies and stabilities with Pt‐cocatalyst over 72 h. Thus, constructing A1‐D‐A2‐D NDI‐based Pdots is a promising approach to developing efficient and stable photocatalysts for solar‐driven hydrogen production.

Organic conjugated polymer dots (Pdots) are considered promising photocatalysts for solar-driven hydrogen production. However, the impact of molecular weight on their photocatalytic activity remains unexplored. In this study, four thiophene-quinoxaline (PTQ)-based Pdots (D-A system) with tunable molecular weights were fabricated to elucidate the effects of molecular weight on Pdot photocatalytic activity. These Pdots serve as highly efficient and stable photocatalysts for visible-light-driven hydrogen generation in a solvent-free organic system, which was achieved for the first time. Low-molecular-weight Pdots exhibited minimal aggregation, small particle sizes, uniform morphology, enhanced charge transfer capability, and superior photocatalytic activity with remarkable photostability. Notably, L-PTQ10 and L-PTQ11 demonstrated exceptional hydrogen evolution rates of 15,807 and 10,411 mu mol g-(1) h-(1), respectively, when coupled with a Pt cocatalyst. The findings from our DFT and molecular dynamics (MD) calculations strongly support our hypothesis, highlighting the use of low-molecular-weight PTQ-based Pdots as a promising strategy to develop efficient and stable photocatalysts for solar-driven hydrogen production. This study presents the synthesis of thiophene-quinoxaline (PTQ)-based polymer dots (Pdots) with tunable molecular weights (D-A system) for the first time. Remarkably, Low-molecular weight Pdots exhibit minimal aggregation, small size, and enhanced charge transfer, leading to superior photocatalytic activity and remarkable photostability.

This study demonstrated the synthesis of imide–imine based COFs, boosting the electrical conductivity in the network due to the presence of dual electron-acceptor centers. This makes them efficient for light-induced hydrogen evolution reactions.

Background: The efficient capture of iodine and the reduction of CO2 emissions has become increasingly important in recent years due to their potential threats to human health and the environment. Hypercrosslinked Porous Organic Polymers (HPPs) are considered excellent adsorbent materials for these purposes due to their high surface areas, controllable structures, and thermal/chemical stabilities. Methods: This work aimed to produce Fe-Bi HPP and An-Bi HPP materials for use in I2 uptake and supercapacitors applications. The preparation of these materials involved utilizing the Friedel-Crafts reaction of Fe-Di imidazole and An-Di imidazole with 4,4 & PRIME;-bis(chloromethyl)-1,1 & PRIME;-biphenyl (Bi-2Cl) in the presence of anhydrous FeCl3. Significant findings: These materials exhibited a narrow range of pore sizes in the micropore range and had a high specific surface area of approximately 850 m2 g-1. According to the results of the electrochemical analysis, the Fe-Bi HPP demonstrated an energy density of 21 Wh Kg-1 and capacitance of 147 F/g. The adsorption experiments demonstrated the effectiveness of both materials in capturing iodine. The Fe-Bi HPP has superior efficiency compared to the An-Bi HPP, which can be attributed to its larger surface area and the presence of the ferrocene unit. It exhibits an impressive I2 adsorption uptake of 112.84 mg g- 1.

The importance of conjugated microporous polymers (CMPs) as active components in photocatalytic hydrogen evolution is growing due to its intense ultraviolet-visible (UV-vis) absorption, potent fluorescence, and high carrier transport capacity, dibenzo[g,p]chrysene shows notable photophysical and electrical features. This is because CMPs have stiff molecular structures with large & pi;-conjugation. In this section, we describe our approach and syntheses of three types of polymers for the first time to determine the reactivity of dibenzo[g,p]chrysene (TBN)-based CMPs for photocatalytic H2 evolution and energy storage applications. Three TBN-based CMPs, TBN-TBN (D-D), TBN-TBN-TPA (A-D), and TBN-TBN-BT (D-A), were synthesized via Sonogashira-Hagihara coupling. TBN-CMP materials were used as working electrodes for energy storage applications. The TBN-TBN-BT CMP demonstrated excellent capacity retention (98.2%) over 2000 cycles and high capacitor (130 F g-1) at 0.5 A g- 1 are in the following order 8452, 9800, and 3060 & mu;mol g - 1h- 1for TBN-TBN, TBN-TBN-TPA, and TBN-TBN-BT CMPs, respectively. These findings suggest that using TBN as an acceptor increases the number of active sites for proton reduction, thereby boosting the rate of H2 evolution. , in accordance with electrochemical performance. Furthermore, the hydrogen evolution rate (HER) results

A sulfide oxidation tuning approach in BDTT is reported for constructing a series of dual acceptor 1-2 (A 1 –A 2 )-type copolymers. PBDTTS-1SO achieved an outstanding HER, demonstrating that the immense potential of the A 1 -A 2 -type polymer photocatalysts.

Photocatalytic water splitting is attracting considerable interest because it enables the conversion of solar energy into hydrogen for use as a zero-emission fuel or chemical feedstock. Herein, we present a universal approach for inserting hydrophilic non-conjugated segments into the main-chain of conjugated polymers to produce a series of discontinuously conjugated polymer photocatalysts. Water can effectively be brought into the interior through these hydrophilic non-conjugated segments, resulting in effective water/polymer interfaces inside the bulk discontinuously conjugated polymers in both thin-film and solution. Discontinuously conjugated polymer with 10 mol% hexaethylene glycol-based hydrophilic segments achieves an apparent quantum yield of 17.82% under 460 nm monochromatic light irradiation in solution and a hydrogen evolution rate of 16.8 mmol m −2 h −1 in thin-film. Molecular dynamics simulations show a trend similar to that in experiments, corroborating that main-chain engineering increases the possibility of a water/polymer interaction. By introducing non-conjugated hydrophilic segments, the effective conjugation length is not altered, allowing discontinuously conjugated polymers to remain efficient photocatalysis.

Organic conjugated polymer dots (Pdots) are emerging as a potential photocatalyst for hydrogen evolution from water. In this work, three organic semiconducting polymer dots (Pdots) based on benzo[d][1,2,3]thiadiazole (isoBT) and surfactant-based poly(ethylene oxide) chains (Triton) are presented as photocatalysts for visible-light-driven hydrogen generation in a completely solvent-free organic system. The resulting Pdots exhibit good photocatalytic activity and excellent photocatalytic stability. Achieving high efficiency with long-term photostability is important for the future commercialization of large-scale hydrogen production. Moreover, PG6 Pdots with a 1-chloro-4-fluorobenzene moiety showed high photocatalytic efficiency with high photocatalytic stability over 100 h. Thus, the introduction of a group with high electronegativity on isoBT-based Pdots is very beneficial for promising photocatalysts in terms of efficiency and stability, even though they could be used in a wide absorption range.

Conjugated polymer dots (Pdots) based on a series of BDT-based polymers with varied biaxially extended side-chain conjugations were prepared and employed for photocatalytic hydrogen production under visible light irradiation from aqueous solutions. The BDT-based polymers consisted of a dithiophedifluorobenzo[c][1,2,5] thiadiazole (DFBT) moiety as the acceptor unit and a BDT unit with different biaxially extended side-chains, including a alkyl-monothienyl group (T), a linear alkyl-dithiophene (2T) group, a branched alkyl-terthiophene (3T) group, and a fused alkyl-benzotrithiophene (B3T) group. The as-prepared Pdots based on these four poly-mers (PBDT-T, PBDT-2T, PBDT-3T, and PBDT-B3T) showed varied photophysical and electrochemical properties along with distinctive photocatalytic activity and long-term stability. Among them, the PBDT-B3T Pdots were showed to deliver a high photocatalytic efficiency of 14.1 mmol g(-1) h(-1) and a superior photocatalytic stability over 375 h in the presence of Pt as cocatalyst and ascorbic acid as sacrificial electron donors. Our results revealed that varying the structures of the biaxially extended side-chains endows a great flexibility in the photocatalytic activity of the polymers and the biaxially-extended conjugated side-chains can be a promising design strategy for the conjugated polymer to enhance the photocatalytic activity and stability.

A library of donor-acceptor system consisting of cyclopentadithiophene-based polymer photocatalysts have been designed and synthesized. Among all photocatalysts, the active PCPDTBSO achieved hydrogen evolution rates of 24.6 mmol h-1 g-1 with apparent quantum yields of 8.7 % at 500 nm. More importantly, combined the results of photocatalytic efficiency, apparent quantum yield, the time-resolved fluorescence decay spectra, the steady-state photoluminescence spectra, and the transient absorption spectroscopy, and the oxidation potentials of sacrificial donors and protons reduction potentials in different pH values, we confirmed the concept that ascorbic acid is a suitable sacrificial donor for narrow bandgap polymers and triethylamine is a suitable sacrificial donor for wide bandgap polymers owing to the existence of the optimal thermodynamic driving force. We believed this study would be advantageous for the selection of photocatalysts and sacrificial donors for hydrogen production.

Organic semiconducting polymers exhibited promising photocatalytic behavior for hydrogen (H2) evolution, especially when prepared in the form of polymer dots (Pdots). However, the Pdot structures were formed using common nonconjugated amphiphilic polymers, which have a negative effect on charge transfer between photocatalysts and reactants and are unable to participate in the photocatalytic reaction. This study presents a new strategy for constructing binary Pdot photocatalysts by replacing the nonconjugated amphiphilic polymer typically employed in the preparation of polymer nanoparticles (Pdots) with a low-molecular-weight conjugated polyelectrolyte. The as-prepared polyelectrolyte/hydrophobic polymer-based binary Pdots truly enhance the electron transfer between the Pt cocatalyst and the polymer photocatalyst with good water dispersibility. Moreover, unlike the nonconjugated amphiphilic polymer, the photophysics and mechanism of this photocatalytic system through time-correlated single-photon counting (TCSPC) and transient absorption (TA) measurements confirmed the Förster resonance energy transfer (FRET) between the polyelectrolyte as a donor and the hydrophobic polymer as an acceptor. As a result, the designated binary Pdot photocatalysts significantly enhanced the hydrogen evolution rate (HER) of 43 900 μmol g-1 h-1 (63.5 μmol h-1, at 420 nm) for PTTPA/PFTBTA Pdots under visible-light irradiation.

Conjugated microporous polymers (CMPs) are promising light harvesters for photocatalytic H2 evolution because they are simple to prepare with various band gaps. To achieve CMPs displaying high photocatalytic performance, appropriate building blocks must be chosen. We prepared four kinds of triphenylpyridine-based CMPs (TPP-CMPs) through reactions with multibrominated monomers having different geometries [1,3,6,8-tetrabromopyrene (pyrene-4Br), pyridine (TPP-3Br), and 1,2,4,5-tetrabromobenzene (BZ-4Br), TPP, and TPP-benzene (BZ) CMPs, respectively]. This strategy allowed effective synthetic regulation of electron enrichment, porosities, and optoelectronic properties of the TPP-CMPs. The surface areas of the TPP-CMPs were high, up to 1370 m2 g-1, and had a high thermal stability. TPP-Py CMP displayed the highest photocatalytic performance with a H2 production rate of 18 100 mu mol g-1 h-1 under irradiation with visible light. Moreover, we achieved apparent quantum yields as high as 22.97% at 420 nm, comparable with those of most other CMPs reported previously.

We designed a series of phenylphosphine oxide derivatives as polymer photocatalysts for visible-light-driven hydrogen evolution. PCzBPO exhibited an excellent HER with a record high AQY of 14.88% at 460 nm.

Given the photocatalytic properties of semiconducting polymers and carbon quantum dots (CQDs), we report a new structure for a metal-free photocatalytic system with a promising efficiency for hydrogen production through the combination of an organic semiconducting polymer (PFTBTA) and N-doped carbon quantum dots (NCQDs) covered by PS-PEGCOOH to produce heterostructured photocatalysts in the form of polymer dots (Pdots). This design could provide strong interactions between the two materials owing to the space confinement effect in nanometer-sized Pdots. Small particle size NCQDs are easy to insert inside the Pdot, which leads to an increase in the stability of the Pdot structure and enhances the hydrogen evolution rate by approximately 5-fold over that of pure PFTBTA Pdots. The photophysics and the mechanism behind the catalytic activity of our design are investigated by transient absorption measurement, demonstrating the role of NCQDs to enhance the charge separation and the photocatalytic efficiency of the PFTBTA Pdot.