Efficient Polymer Research Articles

Morphological Characteristics of Biopolymer Thin Films Swollen-Rich in Solvent Vapors.

Biopolymers exhibit a large variety of attractive properties including biocompatibility, flexibility, gelation ability, and low cost. Therefore, especially in more recent years, they have become highly suitable for a wider and wider range of applications stretching across several key sectors such as those related to food packaging, pharmaceutic, and medical industries, just to name a few. Moreover, biopolymers' properties are known to be strongly dependent on the molecular arrangements adopted by such chains at the nanoscale and microscale. Fortunately, these arrangements can be altered and eventually optimized through a plethora of more or less efficient polymer processing methods. Here, we used a space-confined solvent vapor annealing (C-SVA) method to subject various biopolymers to rich swelling in solvent vapors in order to favor their further crystallization or self-assembly, with the final aim of obtaining thin biopolymer films exhibiting more ordered chain conformations. The results obtained by atomic force microscopy revealed that while the gelatin biopolymer nucleated and then crystallized into granular compact structures, other biopolymers preferred to self-assemble into (curved) lamellar rows composed of spherical nanoparticles (glycogen and chitosan) or into more complex helix-resembling morphologies (phytagel). The capability of the C-SVA processing method to favor crystallization and to induce self-assembly in various biopolymeric species or even monomeric units further emphasizes its great potential in the future structuring of a variety of biological (macro)molecules.

Polybenzimidazole dispersed polymer coated nanowires as efficient electrolytes for proton exchange membrane fuel cells

In this study, polymer-coated anisotropic inorganic nanowires dispersed in PBI matrix were introduced to construct 1D proton conducting channels within PBI. Ionic-liquid and solvothermal methods were used for the synthesis of ZrO2 and W18O49 NWs, which were coated with PVPA and PDDA polymers to increase their proton conductivity. Our results showed that, prepared membranes have amorphous nature due to the dominating presence of PBI. SEM analysis revealed the average thickness of membrane of about 36 µm. TG/DTA analysis detected lower weight loss of W18O49 NWs (total 2.8%) compared to ZrO2 NWs (18%). Proton conductivity analysis showed that, PDDA/W18O49 NWs possess relatively 4 times higher proton conductivity (4×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \ imes $$\\end{document}10−4 Scm−1) compared to PDDA/ZrO2 NWs (1×\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$ \ imes $$\\end{document}10−4 Scm−1) at 80 ℃. In addition, PDDA-coated W18O49 NWs dispersed PBI membranes showed the highest fuel cell current density (1.2 A/cm2) and power density (215 mW/cm2) at 150 ℃ after 24 h which is nearly 2.5 times higher than pure PBI membrane. In addition, they exhibited the lowest in-situ proton resistance of about (0.47 Ω) compared with that of pure PBI membrane (0.8 Ω). Our results are introducing new concepts towards the development of thin and efficient polymer electrolyte membranes for PEM fuel cells.

Electropolymerization of D-A-D type butterfly-shaped monomers based on triphenylamine-thiophene consisting of camphor substituted quinoxaline moiety for efficient electrochromism and supercapacitors

Two new butterfly-shaped monomers TTCQF and TTCQH consisting of camphor-substituted quinoxaline units as π-spacers were designed and synthesized, which were further electrochemical polymerized and deposited on ITO substrates for electrochromic energy storage devices. The present cross-linked polymer thin films PTTCQF and PTTCQH displayed prominent color changes with significant optical contrast in both the visible and near-infrared regions under external electrical stimuli. These two polymers showcased superior electrochromic performance, involving high optical contrast, fast switching speed, and good coloration efficiency. Additionally, both polymers demonstrated a high areal specific capacitance (12 mF/cm2 for PTTCQH and 9.97 mF/cm2 for PTTCQF) at a current density of 0.1 mA/cm2. Electrochromic energy storage devices based on these polymers were fabricated, and not only illuminated an LED bulb but also visually indicated the energy storage state, guaranteed their potential for applications in energy-saving smart windows. This work may provide valuable insights into the development of efficient cross-linked electrochromic energy storage polymers.

Porous Semiconducting Polymer Nanoparticles as Intracellular Biophotonic Mediators to Modulate the Reactive Oxygen Species Balance.

The integration of nanotechnology with photoredox medicine has led to the emergence of biocompatible semiconducting polymer nanoparticles (SPNs) for the optical modulation of intracellular reactive oxygen species (ROS). However, the need for efficient photoactive materials capable of finely controlling the intracellular redox status with high spatial resolution at a nontoxic light density is still largely unmet. Herein, highly photoelectrochemically efficient photoactive polymer beads are developed. The photoactive material/electrolyte interfacial area is maximized by designing porous semiconducting polymer nanoparticles (PSPNs). PSPNs are synthesized by selective hydrolysis of the polyester segments of nanoparticles made of poly(3-hexylthiophene)-graft-poly(lactic acid) (P3HT-g-PLA). The photocurrent of PSPNs is 4.5-fold higher than that of nonporous P3HT-g-PLA-SPNs, and PSPNs efficiently reduce oxygen in an aqueous environment. PSPNs are internalized within endothelial cells and optically trigger ROS generation with a >1.3-fold concentration increase with regard to nonporous P3HT-SPNs, at a light density as low as a few milliwatts per square centimeter, fully compatible with in vivo, chronic applications.

Precisely Controlling Polymer Acceptors with Weak Intramolecular Charge Transfer Effect and Superior Coplanarity for Efficient Indoor All-Polymer Solar Cells with over 27% Efficiency.

Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

β-Triketones as Reactive Handles for Polymer Diversification via Dynamic Catalyst-Free Diketoenamine Click Chemistry.

The spontaneous condensation of amines with β-triketones (TK), forming β,β'-diketoenamines (DKE) and releasing water as the sole byproduct, exhibits many of the hallmarks of "click" reactions. Such characteristics render TKs as a highly advantageous platform for efficient polymer diversification, even in biological contexts. Leveraging reversible addition-fragmentation chain transfer (RAFT) and photoiniferter polymerization of novel TK-containing vinylic monomers, we synthesized polymers containing pendent TKs with excellent control of molecular weights, even in excess of 106 g mol-1. Under mild, catalyst-free conditions, poly(β-triketone methacrylate) could be modified with a diverse scope of amines containing a plethora of functional groups. The high efficiency of this functionalization approach was further emphasized when grafting-to with poly(ethylene glycol)-amine resulting in bottlebrushes with molecular weights reaching 2.0 × 107 g mol-1. Critically, while the formed DKE linkages are stable under ambient conditions, they undergo catalyst-free, dynamic transamination at elevated temperatures, paving the way for associative covalent adaptable networks. Overall, we introduce pendent triketone moieties into methacrylate and acrylamide polymers, establishing a novel postpolymerization modification technique that facilitates catalyst-free ligation of amines under highly permissible conditions.

A highly efficient porphyrin-based azo-porous organic polymer for selective CO2 capture and conversion

The greenhouse gas (GHG) emissions from fossil fuel combustion and carbon dioxide (CO2) cause global warming and climate change. In this study, we synthesized three porphyrin-based azo-porous organic polymers (PBPOP1, PBPOP2, and PBPOP3) that enable the capture and one-step conversion of CO2. These catalysts effectively capture the CO2 molecules over N2 in a post-combustion environment. PBPOP3 exhibited an enhanced CO2/N2 selectivity at 313 K, with a value of 534. We characterized the porphyrin-based azo-POPs catalysts using FT-IR, 13C solid-state NMR, XRD, TGA, and HR-FESEM. We evaluated the gas adsorption properties using Brunauer–Emmett–Teller analysis, which included adsorption–desorption isotherms, NLDFT pore-size distribution, and adsorption at 298, 313, and 353 K. The fixation of CO2 with styrene oxide and phenyl glycidyl ether was performed using catalysts for conversion to styrene carbonate (tetra-n-butylammonium bromide was used as a co-catalyst). Thus, our findings can be used for reducing the amount of CO2 gas in the atmosphere by synthesizing porphyrin-based azo-POP catalysts.

Linker Mediated Electronic-State Manipulation of Conjugated Organic Polymers Enabling Highly Efficient Oxygen Reduction.

Conjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure-performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc-CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc-CPs) are judiciously crafted via in situ assembling square-planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde-based organic linkers in the presence of CNTs. Intriguingly, upon varying the electronic characteristic of organic linkers from terephthalaldehyde (TA) to 2,5-thiophenedicarboxaldehyde (TDA) and then to thieno/thiophene-2,5-dicarboxaldehyde (bTDA), their corresponding CNTs@CoPc-CPs exhibit gradually improved electrocatalytic ORR performance. More importantly, theoretical calculations reveal that the charge transfer from CoPc units to electron-withdrawing linkers (i.e., TDA and bTDA) drives the delocalization of Co d-orbital electrons, thereby downshifting the Co d-band energy level. Accordingly, the active Co centers with more positive valence state exhibit optimized binding energy toward ORR-relevant intermediates and thus a balanced adsorption/desorption pathway that endows significant enhancement in electrocatalytic ORR. This work demonstrates a molecular-level engineering route for rationally designing efficient polymer catalysts and gaining insightful understanding of electrocatalytic mechanisms.

Linker Mediated Electronic‐State Manipulation of Conjugated Organic Polymers Enabling Highly Efficient Oxygen Reduction

AbstractConjugated polymers with tailorable composition and microarchitecture are propitious for modulating catalytic properties and deciphering inherent structure‐performance relationships. Herein, we report a facile linker engineering strategy to manipulate the electronic states of metallophthalocyanine conjugated polymers and uncover the vital role of organic linkers in facilitating electrocatalytic oxygen reduction reaction (ORR). Specifically, a set of cobalt phthalocyanine conjugated polymers (CoPc‐CPs) wrapped onto carbon nanotubes (denoted CNTs@CoPc‐CPs) are judiciously crafted via in situ assembling square‐planar cobalt tetraaminophthalocyanine (CoPc(NH2)4) with different linear aromatic dialdehyde‐based organic linkers in the presence of CNTs. Intriguingly, upon varying the electronic characteristic of organic linkers from terephthalaldehyde (TA) to 2,5‐thiophenedicarboxaldehyde (TDA) and then to thieno/thiophene‐2,5‐dicarboxaldehyde (bTDA), their corresponding CNTs@CoPc‐CPs exhibit gradually improved electrocatalytic ORR performance. More importantly, theoretical calculations reveal that the charge transfer from CoPc units to electron‐withdrawing linkers (i.e., TDA and bTDA) drives the delocalization of Co d‐orbital electrons, thereby downshifting the Co d‐band energy level. Accordingly, the active Co centers with more positive valence state exhibit optimized binding energy toward ORR‐relevant intermediates and thus a balanced adsorption/desorption pathway that endows significant enhancement in electrocatalytic ORR. This work demonstrates a molecular‐level engineering route for rationally designing efficient polymer catalysts and gaining insightful understanding of electrocatalytic mechanisms.

Highly Efficient and Thermally Durable Luminescence of 1D Eu3+ Coordination Polymers with Arsenic Bridging Ligands.

In this work, bisarsine oxides were evaluated as novel bridging ligands, aiming to develop practical and efficient luminescent lanthanide coordination polymers. We have synthesized one-dimensional (1D) Eu3+ coordination polymers that incorporate bisarsine oxide bridging ligands and hexafluoroacetylacetonate anions. These polymers exhibited a denser packing of chains compared to analogous polymers bridged with bisphosphine oxides. The coordination polymers demonstrated exceptional thermal stability and substantial emission quantum yields. Additionally, the bisarsine oxides induced a pronounced polarization effect, facilitating a sensitive electric dipole transition that yields considerably narrow band red emission. Remarkably, the Eu3+ coordination polymers with bisarsine oxides maintained intense emission even at 550 K. A distinctive feature of these polymers is their heating-induced emission enhancement observed when the temperature was increased from 300 K to 400 K.

Thermally Induced Phase Separation of the PEDOT:PSS Layer for Highly Efficient Laminated Polymer Light-Emitting Diodes.

Among various conductive polymers, the poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) film has been studied as a promising material for use as a transparent electrode and a hole-injecting layer in organic optoelectronic devices. Due to the increasing demand for the low-cost fabrication of organic light-emitting diodes (OLEDs), PEDOT:PSS has been employed as the top electrode by using the coating or lamination method. Herein, a facile method is reported for the fabrication of highly efficient polymer light-emitting diodes (PLEDs) based on a laminated transparent electrode (LTE) consisting of successive PEDOT:PSS and silver-nanowire (AgNW) layers. In particular, thermally induced phase separation (TIPS) of the PEDOT:PSS film is found to depend on the annealing temperature (Tanneal) during preparation of the LTE. At Tanneal close to the glass transition temperature of the PSS chains, a PSS-rich phase with a large number of PSS- molecules enhances the work function of the PEDOT:PSS on the glass-side surface relative to the air side. By using the optimized LTEs, bidirectional laminated PLEDs are obtained with a total external quantum efficiency of 2.9% and a turn-on voltage of 2.6 V, giving a comparable performance to that of the reference bottom-emitting PLED based on a costly evaporated metal electrode. In addition, an analysis of the angular characteristics, including the variation in the electroluminescence spectra and the change in luminance according to the emission angle, indicates that the laminated PLED with the LTE provides a more uniform angular distribution regardless of the direction of emission. Detailed optical and electrical analyses are also performed to evaluate the suitability of LTEs for the low-cost fabrication of efficient PLEDs.

Cellulose-based eutectogel electrolyte with high ionic conductivity for solid-state lithium-ion batteries

It is known that the low ionic conductivity of solid-state polymer electrolytes at room temperature (RT) has severely restricted their practical application in lithium-ion batteries. Although eutectogel (ETG) electrolytes could solve this problem to some extent, highly compatible deep eutectic solvent (DES)/polymer systems are desirable to further enhance ion conduction. Herein, we designed cellulose-based ETG (CETG) with dual channels through “hopping” and “vehicle” mechanisms by hydroxyethyl cellulose (HEC) molecular chains and N-methylacetamide (NMA)/LiTFSI-derived DES, respectively. Thanks to the strong molecular interactions between HEC and DES, the highest DES content in the ETG could achieve 90 %, which endowed the CETG with an excellent ionic conductivity of 2.04 × 10–3 S cm−1 at 30 °C. Additionally, our designed CETG displayed good self-healing and fire retardant properties. The assembled Li/LiFePO4 cell showed a capacity retention of 91.8 % after 200 cycles at 0.2 C under RT with an initial discharge capacity of 156.2 mAh g−1. In particular, the capacity retention rates of the assembled batteries reached 95.2 % and 92.1 %, respectively, after 100 cycles at 0.2 C under 60 °C and 50 cycles at 0.2 C under 100 °C. Our fabrication strategy would provide a novel idea for the design of green, safe and efficient solid-state polymer electrolytes for lithium-ion batteries.

A benzobisoxazole-based polymer assisting high efficiency polymer solar cells

Ternary strategy is an effective method to optimize photovoltaic process and improve device performance. In this work, a benzobisoxazole-based conjugated polymer PBBO was designed and employed as the guest component for PM6:BTP-eC9 based devices. The polymer PBBO shows a large band gap of 2.16 eV and strong photoluminescence property, with efficient energy transfer observed between PBBO and PM6. The ternary blends not only form a cascaded energy level distribution, but also an alloy-like structure, which can effectively promote the exciton dissociation, charge transfer and efficiently suppress charge recombination. As a result, the power conversion efficiency (PCE) of the ternary device is substantially improved from 17.50% to 18.66% with the incorporation of PBBO guest component. Meanwhile, the ternary device shows good stability with retaining 86% of initial efficiency after storage for 2000 hours. This research demonstrates that the polymer PBBO would be an excellent photovoltaic material to optimize the performance of polymer solar cells.

Effect of reduced graphene oxide on thermal property of recycled textile polyamide

This study explored the impact of reduced graphene oxide (rGO) addition on the thermal properties of recycled polyamide (PARec) obtained from repurposed textile industry microfibers initially earmarked for landfill disposal. Characterization of PARec involved techniques like differential scanning calorimetry (DSC), thermogravimetric analysis (TG), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). RGO was characterized through Raman spectroscopy, scanning electron microscopy (SEM), and X-ray diffraction (XRD). Mixtures with varying rGO concentrations, such as PARec-1 (0.1% rGO), PARec-5 (0.5% rGO), and PARec-10 (1% rGO), were prepared and processed in a twin-screw extruder. SEM images at PARec show good dispersion of rGO in the polymer matrix. Thermal properties were determined via DSC and TG, revealing the presence of polyamide 6 in PARec-0 and indicating rGO's quality. Notably, PARec-10 exhibited a slight 3.8% increase in melting temperature and a 7.5% rise in crystallization temperature. These results suggest the potential for improved thermal properties with rGO incorporation. The study contributes to understanding polymer blend thermal properties and introduces an innovative, efficient polymer waste recycling method aligned with sustainability principles.

Delaying the First Nucleation Event of Amorphous Solid Dispersions Above the Polymer Overlap Concentration (c*): PVP and PVPVA in Posaconazole

A thorough understanding of effects of polymers on crystallization of amorphous drugs is essential for rational design of robust amorphous solid dispersion (ASD), since crystallization of the amorphous drug negates their solubility advantage. In this work, we measured the first nucleation time (t0, time to form the first critical nucleus in fresh liquid/glass) in posaconazole (POS)/polyvinylpyrrolidone vinyl acetate (PVPVA) and POS/polyvinylpyrrolidone (PVP K25) ASDs and showed that the polymer overlap concentration (c*, concentration above which adjacent polymer chains begin to contact) is critical in controlling crystallization of ASDs. When polymer concentration c < c*, t0 of POS ASDs is approximately equal to that of the neat amorphous POS, but it increases significantly when c > c*. This observation supports the view that the effective inhibitory effect of crystallization in ASDs above c* is primarily correlated with delay in the first nucleation event. Our finding is useful in efficient polymer selection and performance prediction of high drug loaded ASD formulations.

Cost-effective polymer donors based on pyridine for efficient nonfullerene polymer solar cells

Developing cost-effective polymer donors that can match nonfullerene acceptors is very important for practical applications of polymer solar cells (PSCs). In this work, low-cost 3-fluoropyridine and pyridine were employed as acceptor unit cores to construct cost-effective polymers PBDT-FPy, PBDT-Py and PBDF-Py by copolymerizing with commercially available donor units. PBDT-FPy, PBDT-Py and PBDF-Py show wide-bandgap of 2.08, 2.15 and 2.05 eV, respectively. Due to the strong electronegativity of nitrogen atom in pyridine and Nδ− … Hδ+ noncovalent dipole-dipole interactions, all polymers exhibit deep-lying highest-occupied molecular orbital (HOMO) energy levels, strong intermolecular π-π interaction and good planarity. The PBDT-FPy: Y6 based device exhibits a power conversion efficiency (PCE) of 8.34%, while the performance of PBDT-Py: Y6 and PBDF-Py: Y6 devices was significantly improved, with PCE of 10.02% and 10.00%. The results indicate that pyridine with simple structure and low synthetic cost is a promising building block to construct high-performance cost-effective polymer donors for application in PSCs.

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Polymer donors with hydrophilic side-chains enabling efficient and thermally-stable polymer solar cells by non-halogenated solvent processing

Efficient triisopropylsilylethynyl-substituted benzo[1,2-b:4,5-b′]dithiophene-based random terpolymers enable non-fullerene organic solar cells with enhanced efficiency

Recent work has highlighted the pivotal role of ternary random polymers in the development of efficient high-performance polymer donors for organic solar cells (OSCs) and most of these D-A copolymer donors are so far constituted of an equal proportion of D and A-units. In this contribution, we report series of PM6-based ternary random terpolymers with unequal D- and A-units, namely, PM-TIPS10, PM-TIPS20 and PM-TIPS20, respectively by adding the 10%, 20% and 30% of simple and low-cost triisopropylsilylethynyl-substituted benzo[1,2-b:4,5-b′]dithiophene (BDT-TIPS) unit as second donor (D1) unit in polymer backbone based on D1-A-D2-A molecular design. Ascribed from the structural similarity of the two building blocks in the terpolymer backbone, these polymers showed orderly molecular packing, broadened light absorption, and the face-on orientation of the active layer to facilitate charge transport. Additionally, the new polymers displayed much deeper highest occupied molecular orbital (HOMO) energy levels than host PM6 polymer, which helped in enhancing the open circuit voltage (Voc) in the PM-TIPS-based OSCs. As a result, when combined with BTP-eC9 acceptor unit, PM-TIPS10 and PM-TIPS20 displayed best efficiency of 16.7 and 16.5% with a small energy loss of 0.484 and 0.473 eV, producing overall superior device parameters compared to PM6-based devices tested parallelly (PCE of 15.7%). This study reveals the correlation between introduction of the BDT-TIPS unit on polymer properties and photovoltaic performance and thus contributes to the design of high-PCE polymer donors by adapting a ternary random copolymerization strategy.

High-performance nonfullerene polymer solar cells based on chlorinated quinoxaline copolymer with a high short-circuit current density

In organic solar cells, the absorption range and extinction coefficient of the active layer not only affect the charge separation and carrier transfer efficiency of excitons, but also influence the JSC, and thus the device efficiency. Herein, an efficient nonfullerene polymer solar cells (NF–PSCs) based on a medium-bandgap (MBG) polymer donor PBDTTS-TClQx comprising chlorinethiophene quinoxaline (Qx) unit and a small molecule nonfullerene acceptor (SM-NFA) Y6 is developed. The PBDTTS-TClQx shows a strong absorption in the wavelength region of 330∼750 nm with an optical band gaps (Egopt) of 1.68 eV, which is well complementary with that of Y6 (1.33 eV) and facilitates achieving of high short-circuit current (JSC) in PSCs. As a result, the PBDTTS-TClQx:Y6-based PSCs achieved a power conversion efficiency (PCE) of 14.28% with a JSC of 25.9 mA cm−2. The JSC of 25.9 mA cm−2 achieved is among the highest reported for Qx-based polymer donors in PSCs.

In-situ formatting donor-acceptor polymer with giant dipole moment and ultrafast exciton separation

Donor-acceptor semiconducting polymers present countless opportunities for application in photocatalysis. Previous studies have showcased their advantages through direct bottom-up methods. Unfortunately, these approaches often involve harsh reaction conditions, overlooking the impact of uncontrolled polymerization degrees on photocatalysis. Besides, the mechanism behind the separation of electron-hole pairs (excitons) in donor-acceptor polymers remains elusive. This study presents a post-synthetic method involving the light-induced transformation of the building blocks of hyper-cross-linked polymers from donor-carbon-donor to donor-carbon-acceptor states, resulting in a polymer with a substantial intramolecular dipole moment. Thus, excitons are efficiently separated in the transformed polymer. The utility of this strategy is exemplified by the enhanced photocatalytic hydrogen peroxide synthesis. Encouragingly, our observations reveal the formation of intramolecular charge transfer states using time-resolved techniques, confirming transient exciton behavior involving separation and relaxation. This light-induced method not only guides the development of highly efficient donor-acceptor polymer photocatalysts but also applies to various fields, including organic solar cells, light-emitting diodes, and sensors.