Fast Charge Separation Research Articles

Color-Tunable Delayed Fluorescence and Efficient Spin–Orbit Charge Transfer Intersystem Crossing in Compact Carbazole-Anthracene-Bodipy Triads Employing the Sequential Electron Transfer Approach

Spin–orbit charge transfer intersystem crossing (SOCT-ISC) is a promising approach to develop heavy-atom-free triplet photosensitizers. However, designing a strong visible-light harvesting heavy-atom-free triplet photosensitizer with efficient ISC ability in various solvents is still challenging. Most of the SOCT-ISC triplet photosensitizers exhibit efficient ISC only in solvent of particular polarity. To address this challenge, herein, two triads (BDP-AN-C-CZ and BDP-AN-N-CZ), composed of carbazole (CZ), anthracene (AN), and bodipy (BDP) moieties, were devised. In these triads, the distance, relative orientation, and position of CZ with respect to the AN moiety were varied to study the effect on photophysical properties, especially on SOCT-ISC efficiency. Electrochemical studies, steady-state, and time-resolved spectroscopies confirmed a sequential photoinduced electron transfer (PET) process in the triads. The fluorescence of the BDP moiety is quenched and a red-shifted CT emission band is observed in the triads, due to the enhanced PET effect, compared to the reference BDP-AN dyad. We observed that the SOCT-ISC yield can be enhanced taking advantage of sequential electron transfer. The triad BDP-AN-C-CZ, in which the CZ moiety was directly linked to the AN moiety, shows an efficient ISC ability both in low-polarity and high-polarity solvents, and unity triplet quantum yield (ΦT) was observed in dichloromethane. Femtosecond transient absorption spectroscopy confirmed the fast charge separation process (1.8 ps) in BDP-AN-C-CZ as compared to the other triad BDP-AN-N-CZ (4.8 ps) and the reference BDP-AN dyad (7.7 ps). The triads were used as triplet photosensitizers for triplet–triplet annihilation (TTA) upconversion, and high upconversion quantum yield (ΦUC = 18%) was observed. Interestingly, long-lived (τDF = 118 μs) and solvent-dependent color-tunable TTA delayed fluorescence was observed in the case of BDP-AN-C-CZ.

Polyethylene glycol (PEG)-modified Ag/Ag2O/Ag3PO4/Bi2WO6 photocatalyst film with enhanced efficiency and stability under solar light

Bi2WO6 photocatalyst possesses great photocatalytic properties, modification with Ag, Ag2O, and Ag3PO4 further improve its photocatalytic activity. Photocatalyst utilized as suspended powders in wastewater treatment imposes restrictions for practical application. Therefore, the design and fabrication of photocatalyst film with high efficiency and stability are crucial for practical application. In this study, polyethylene glycol (PEG) modified AP-BWO (A: Ag, Ag2O; P: Ag3PO4; BWO: Bi2WO6) photocatalyst film coated on glass substrate was firstly synthesized with excellent photocatalytic activity and stability. Bi2WO6based films were modified with different PEG molecular weight, dosage and coating layers, followed by characteristic analysis (SEM, TEM, XPS, UVvis, PL, and photocurrent density) and photodegradation test. Photodegradation showed that 2-layered of 12 g L−1 PEG2000 modified AP-BWO film exhibited the highest photocatalytic activity. XPS and TEM indicated that PEG2000-AP-BWO film was fabricated successfully. SEM and UV–vis denoted the photocatalyst film showed small particle size and strong visible-light absorption. Furthermore, PL and photocurrent density confirmed its low recombination and fast charge separation of electronhole pairs. The photocatalytic films showed high activity and stability in both 10-cycle repeatability experiments and tandem-type photocatalytic recycle system. Therefore, PEG2000-AP-BWO film with enhanced photocatalytic performance and stability was a promising alternative for wastewater treatment.

Facile synthesis of porous C-doped C3N4: fast charge separation and enhanced photocatalytic hydrogen evolution

A facile gaseous-bubbles templating approach to synthesize porous C-doped g-C3N4 with enhanced photocatalytic activity for hydrogen evolution reaction.

A high-performance silicon photoanode enabled by oxygen vacancy modulation on NiOOH electrocatalyst for water oxidation.

Silicon (Si) is an attractive photoanode material for photoelectrochemical (PEC) water splitting. However, Si photoanode towards the oxygen evolution reaction (OER) is highly challenged due to its poor stability and catalytic inactivity. The integration of highly active electrocatalysts with Si photoanodes has been considered to be an effective strategy to improve their OER performance by accelerating the reaction kinetics and inhibiting Si photocorrosion. In this work, ultra-small NiFe nanoparticles are deposited onto the n-Si/Ni/NiOOH surface to improve the activity and stability of Si photoanodes by engineering the electrocatalyst and Si interface. Ultra-small NiFe nanoparticles can introduce oxygen vacancies via modulating the local electronic structure of Ni hosts in NiOOH electrocatalysts for fast charge separation and transfer. Besides, NiFe nanoparticles can also serve as a co-catalyst exposing more active sites and as a protection layer preventing Si photocorrosion. The as-prepared n-Si/Ni/NiOOH/NiFe photoanode exhibits excellent OER activity with an onset potential of 1.0 V versus reversible hydrogen electrode (RHE) and a photocurrent density of ∼25.2 mA cm-2 at 1.23 V versus RHE. This work provides a promising approach to design high-performance Si photoanodes by surface electrocatalyst engineering.

Role of graphene and transition metal dichalcogenides as hole transport layer and counter electrode in solar cells

Photovoltaic (PV) technology got much attention in the past few decades in developing advanced and environment friendly solar cells (SCs). However, high cost, unstable nature, and low efficiency are major limitations towards commercialization of SCs. To overcome the issues, two-dimensional materials (2DMs) have been exploited due to low cost, high catalytic activity, fast charge separation, and better electrochemical performance. The review emphasis on (a) the electrochemical performance of graphene and transition metal dichalcogenides (TMDCs) as a hole transport layer (HTL) in SCs and (b) to explore low-cost and effective counter electrode (CE) based on graphene and TMDCs for dye-sensitized solar cell (DSSC). The review presents a comparative analysis of 2DMs as HTL and CE to attain highly efficient and low-cost PV devices. Multiple combinations of the material with graphene, graphene oxide (GO), reduced graphene oxide (rGO), tungsten disulfide (WS2), molybdenum disulfide (MoS2) as HTL, and CE material in PV cells are discussed and comparatively analyzed. Numerous strategies are briefly discussed to enhance the efficiency of SCs by utilizing graphene and TMDCs based HTL and CEs. The review focuses on the recent progress in developing low-cost and highly efficient PV devices by using 2DMs. Our study reveals that GO/PEDOT:PSS demonstrate a maximum power conversion efficiency (PCE) of 13.1% when fabricated at different revolutions. Moreover, our statistical analysis unveils that efficiency of the cell can be enhanced by optimizing the layer thickness, which provide a route to develop highly efficient and better performance SCs that can be exploited for future commercial applications.

High-efficient precious-metal-free g-C3N4-Fe3O4/β-FeOOH photocatalyst based on double-heterojunction for visible-light-driven hydrogen evolution

The two-dimensional (2D) g-C3N4 has a wide application prospect in photocatalysis field due to its larger surface reactions, wider absorption of light and faster charge separation. However, the lack of active site of reduction leads to its poor hydrogen evolution reaction (HER) activity. In this work, the intermediate β-FeOOH was synthesized as a high-efficiency precious metal free co-catalyst in hydrogen production. Then, the g-C3N4-Fe3O4/β-FeOOH (CNFF-x,y, x = 1, 2 and 3, y denotes the reaction time (h)) photocatalyst based on p-n and Z-scheme heterojunction was constructed via a subsequent solvothermal process. The chemical composition, microtopography, crystallography, photochemical and electrochemical properties of the CNFF-x,y were analyzed by XRD, FI-IR, TEM, XPS and so on. The visible-light-driven (VLD) catalytic performance of CNFF-x,y heterojunction was evaluated by the hydrogen evolution reaction (HER). Results showed that CNFF-2,10 photocatalyst based on p-n (g-C3N4-Fe3O4) and Z-scheme (Fe3O4/β-FeOOH) heterojunction presented the highest VLD catalytic HER activity (33.25 μmol g−1 h−1) at the absence of Pt co-catalyst after illumination for 6 h. It indicated that the effective introduction of Fe3O4/β-FeOOH nanoparticles (NPs) into g-C3N4 to construct double-heterojunction (g-C3N4-Fe3O4/β-FeOOH) could greatly broaden the light response property and inhibit the recombination of photo-induced carriers, exhibiting enhanced HER activity. Meanwhile, this double-heterojunction photocatalyst presented robust photostability and reproducibility even been used several times. The findings of an intermediate β-FeOOH were put forward in this study will provide some new ideas for the research of HER.

Achieving Fast Charge Separation and Low Nonradiative Recombination Loss by Rational Fluorination for High-Efficiency Polymer Solar Cells.

Four low-cost copolymer donors of poly(thiophene-quinoxaline) (PTQ) derivatives are demonstrated with different fluorine substitution forms to investigate the effect of fluorination forms on charge separation and voltage loss (Vloss ) of the polymer solar cells (PSCs) with the PTQ derivatives as donor and a A-DA'D-A-structured molecule Y6 as acceptor. The four PTQ derivatives are PTQ7 without fluorination, PTQ8 with bifluorine substituents on its thiophene D-unit, PTQ9, and PTQ10 with monofluorine and bifluorine substituents on their quinoxaline A-unit respectively. The PTQ8- based PSC demonstrates a low power conversion efficiency (PCE) of 0.90% due to the mismatch in the highest occupied molecular orbital (HOMO) energy levels alignment between the donor and acceptor. In contrast, the devices based on PTQ9 and PTQ10 show enhanced charge-separation behavior and gradually reduced Vloss , due to the gradually reduced nonradiative recombination loss in comparison with the PTQ7-based device. As a result, the PTQ10-based PSC demonstrates an impressive PCE of 16.21% with high open-circuit voltage and large short-circuit current density simultaneously, and its Vloss is reduced to 0.549 V. The results indicate that rational fluorination of the polymer donors is a feasible method to achieve fast charge separation and low Vloss simultaneously in the PSCs.

CdS quantum dots/Au nanoparticles/ZnO nanowire array for self-powered photoelectrochemical detection of Escherichia coli O157:H7

In this paper, the hydrothermally grown ZnO nanowire array (NWs) was modified by Au nanoparticles (NPs) and CdS quantum dots (QDs) to construct a high-performance photoelectrochemical (PEC) electrode. The aligned ZnO NWs, which decorated Au NPs and CdS QDs have the effective light absorption range from UV to visible region. This hybrid structure provided a self-powered PEC electrode with a favorable energy-band configuration for fast charge separation and transportation. Meanwhile, the Au NPs and CdS QDs also made increase of the surface area to improve the immobilization of the analytes. After assembling aptamer as recognition element, this composite nanoarray was further developed as a self-powered PEC biosensor by synergizing above multiple enhancement factors. The PEC aptasensor exhibited a rapid response in a wide linear range of 10–107 CFU/mL with the detection limit as low as 1.125 CFU/mL to Escherichia coli O157:H7 (E. coli O157:H7). This approach would offer an alternative PEC transduction for fast environment monitoring and clinical diagnosis related to pathogenic bacteria.

Ga-Doped AgInS2 Modified with Co–Pi Co–catalyst for Efficient Photoelectrochemical Water Splitting

In this work, AgInS2 photoelectrodes doped with Ga element and deposited Co–Pi co–catalyst have been prepared on FTO substrates by hydrothermal and electrochemical deposition methods. In photoelectrochemical (PEC) measurements, the photocurrent density of AgInS2/Ga5%/Co–Pi photoelectrodes (2.18 mA/cm2 at 1.2 V vs. RHE) is about 3.25 times higher than that of pure AgInS2 photoelectrodes (0.67 mA/cm2 at 1.2 V vs. RHE). The enhanced PEC performance could be ascribed to the improved light absorption by doping Ga element and fast charge separation by depositing Co–Pi co–catalyst. This work highlights that doping appropriate metal element and loading co-catalyst to synergistically modify photoelectrodes are practicable approach for PEC water splitting.

Assessment of clean H2 energy production from water using novel silicon photocatalyst

Nanosheets of silicon have attracted a great deal of attention due to its tunable optical and electronic properties. However, the development of facile and easily scalable synthesis process has remained a great contest. Endeavor has been made in this research to find a waste inferred effective photocatalyst to deliver hydrogen (H2) through visible light responsive water splitting. One-pot solid phase reaction was applied to synthesis catalyst and adopted ultrathin structure. The photocatalytic efficiency of catalyst was examined by XRD, XPS, and UVeVIS absorption spectra, PL, FESEM, HRTEM and EDX. The HRTEM and FESEM images revealed the interconnected nanosheets with Si having the average thickness of 5 nm and their band gaps were 2.3e2.5 eV corresponding to the absorption of visible light range. The H2 production rate on photocatalyst was originated to 3200 mmol h�1 without utilizing any conciliatory electron givers, voltage or pH alteration, which beats the Pt, Ru, Rh, Pd and Au stacked photocatalyst ever detailed up until this point. The significant increase in photocatalytic activity could be the fast charge migration and separation from the silicon-hydrogen and siliconhydroxyl bonds on Si surface and facilitation of charge separation could results from the multiple reflections of visible light on ultrathin nanosheets. It has been confirmed that the electron/hole recombination rate in ultrathin nanosheets of Si declined due to the oxidation of Si surface. It would be presumed that the approach of surface chemistry of silicon could not be limited towards the photocatalytic water splitting and could be applicable to remedy water pollution.

One-step synthesis of novel K+ and cyano groups decorated triazine-/heptazine-based g-C3N4 tubular homojunctions for boosting photocatalytic H2 evolution

Constructing homojunctions with different morphologies, exposing facets, crystal phases or semiconductor types in a photocatalyst is an essential approach to boost the photoactivity. Herein, the g-C3N4 phase homojunctions decorated with cyano groups and K+ were designed and successfully synthesized via only adjusting the reaction temperatures within a facile one-step molten salt route. Such unique junctions were constructed through the overgrowth of triazine-based g-C3N4 nanoparticles embedded in the surface and inner wall of heptazine-based g-C3N4 hollow tubes. Benefited from the multiple advantages of high specific surface area, unique tubular structure, enhanced visible light absorption, and fast charge transfer and separation, the triazine-/heptazine-based g-C3N4 homojunctions drastically enhanced the photocatalytic hydrogen production performance, achieving a 2 and 12-fold improvement than the pristine g-C3N4 microtube and bulk g-C3N4, respectively. This study provides an in-depth insight into the design and fabrication of other g-C3N4-based photocatalysts for more efficient solar energy conversion applications.

Phase-Selective Disordered Anatase/Ordered Rutile Interface System for Visible-Light-Driven, Metal-Free CO2 Reduction.

Visible-light-driven photocatalytic CO2 reduction using TiO2 that can absorb light of all wavelengths has been sought for over half a century. Herein, we report a phase-selective disordered anatase/ordered rutile interface system for visible-light-driven, metal-free CO2 reduction using a narrow band structure, whose conduction band position matches well with the reduction potential of CO2 to CH4 and CO. A mixed disordered anatase/ordered rutile (Ad/Ro) TiO2 was prepared from anatase and rutile phase-mixed P25 TiO2 at room temperature and under an ambient atmosphere in sodium alkyl amine solutions. The Ad/RoTiO2 showed a narrow band structure due to multi-internal energy band gaps of Ti3+ defect sites in the disordered anatase phase, leading to high visible light absorption and simultaneously providing fast charge separation through the crystalline rutile phase, which was faster than that of pristine P25 TiO2. The band gap of Ad/Ro TiO2 is 2.62 eV with a conduction band of -0.27 eV, which matches well with the reduction potential of -0.24 VNHE of CO2/CH4, leading to effective electron transfer to CO2. As a result, the Ad/Ro TiO2 provided the highest CH4 production (3.983 μmol/(g h)), which is higher than that of even metal (W, Ru, Ag, and Pt)-doped P25, for CO2 reduction under visible light.

Synthesis of hierarchically mesoporous polymeric carbon nitride with mesoporous melamine as a precursor for enhanced photocatalytic performance

Constructing mesoporous structure in polymeric carbon nitride (CN) is an effective way to enhance the photocatalytic performance, but rare work achieved this through controlling morphologies of raw materials because of their easy fusion on calcination. Herein, mesoporous melamine (MMA) comprising nanorods was prepared via facile acid processing on commercial MA (CMA), with ~40 times increased specific surface area. By jointly using MMA and the gas template (NH4Br) as the precursor for the first time, hierarchically mesoporous CN (HMCN) was simply synthesized with much thinner nanosheets, ~4 times higher specific surface area, stronger photoabsorption, and faster charge separation than bulky CN. On this account, HMCN exhibits much higher photoactivity in H2 production and for environmental purification. Its visible-light photocatalytic H2 evolution rate, 1412 μmol g–1 h−1 is ~8.9 times that of bulky CN, and reactive oxygen species generation rates are prominently higher than those of CN. The chemical stability of HMCN in the photoreactions is satisfactory. This work provides a simple way to prepare MMA and a novel strategy to synthesize HMCN, which may guide synthesis of other mesoporous CN-based photocatalysts.

Heterogeneous structural defects to prompt charge shuttle in g-C3N4 plane for boosting visible-light photocatalytic activity

Structural defect engineering toward g-C3N4 plane usually has great benefit on modulating electron structure and photocatalytic performance. Here, we report a porous g-C3N4 material with heterogeneous structural defects, oxygen atom replacing edge nitrogen and cyano group, obtained via a facile treatment method. The reconstructed material shows narrowing band gap, high light absorption and fast charge separation. Theoretical calculation discloses that the doped oxygen atom and the nearby atoms accept electrons as reduction site to produce hydrogen, while the undoped fraction and cyano group take the duty to oxidize water. The delocalization of reactive sites drives charge shuttle on the plane, limiting recombination of charge carriers. Consequently, the modified g-C3N4 shows excellent photocatalytic activity with apparent quantum efficiency of 8.41% under 420 nm wavelength, surpassing pure g-C3N4 and other reported materials with defect compilation. We think that this work provides a new avenue to understand the function of structural defect on prompt charge separation.

Porphyrin-Based Conjugated Polymers as Intrinsic Semiconducting Photocatalysts for Robust H2 Generation under Visible Light

Up to now, conjugated organic polymers as organic semiconductors have received more and more attention on the direct conversion of water to hydrogen energy. Herein, we designed and synthesized a series of porphyrin-based conjugated polymers (Zn-ZnDETPP, Co-CoDETPP, and Zn-CoDETPP) with intrinsic semiconducting feature and broad spectral response ability. The Zn-CoDETPP polymer exhibits a photocatalytic H2 generation activity (43 μmol h–1) illuminated by λ ≥ 400 nm light and a record apparent quantum yield (7.36%) at λ = 400 nm monochromatic light among those porphyrin-based polymers reported previously, while the Zn-ZnDETPP and Co-CoDETPP only deliver a H2 generation activity of 8.0 and 33 μmol h–1 respectively. The characteristic results demonstrate that the CoDETPP porphyrin units as bridges in the Zn-CoDETPP polymer can act as an electron acceptor and promote the metal-to-metal charge transfer (MMCT) from zinc porphyrin to cobalt porphyrin units, which could lead to more effective and faster charge separation in the Zn-CoDETPP polymer for the H2 generation reaction. The present results open up a promising strategy applying porphyrin-based conjugated polymers as intrinsic semiconductors for efficient H2 generation and instruct us to efficiently convert solar energy into chemical energy by molecular designing.

Linkage dependence of charge separated lifetime in small donor-acceptor dyads system

Fast charge separation (CS) process and slow charge recombination (CR) process are critical for effective utilization of solar energy in artificial photosynthesis, photocatalysis and organic photovoltaic devices. Here we demonstrated in a model donor-acceptor (D-A) dyad of styrene based triphenylamine derivative (MTPA) as an electron donor (D), triazine group (TRC) as an electron acceptor (A) (MTPA-TRC) that the CS and CR process can be modulated by the linker groups between donor and acceptor. We synthesized a series of flexibly linked D-A dyads MTPA-TRC-n with different length of methylene units (n = 1, 2, 3, n stands for the number of methylene units) as the spacer and lifetimes of charge-separated states ranging from nanoseconds to milliseconds were observed. According to the Marcus charge transfer theory, MTPA-TRC-n have similar reorganization energies (λ) but decreased electronic coupling matrix element (V). V value is the key factor to dominate the charge transfer rate and charge-separated lifetime in this D-A dyads system. Additionally, the decay coefficient (β) of length dependence of electron transfer rate was decreased from 0.4 Å−1 to 0.3 Å−1 in methanol compared to acetonitrile. It revealed that electronic coupling between the donor and acceptor could be enhanced by the increasing solvent polarity in the non-conjugated linked D-A system.

Molecularly imprinted Ag/Ag3VO4/g-C3N4 Z-scheme photocatalysts for enhanced preferential removal of tetracycline

High selectivity and fast charge separation are two important factors for photocatalytic wastewater treatment. Herein, we prepared a molecular imprinted Ag/Ag3VO4/g-C3N4 photocatalyst (MIP) that exhibited great specific recognition ability along with excellent photocatalytic activity. The ultrathin g-C3N4 nanosheets with high surface are used to prepare. The Z-scheme Ag3VO4/g-C3N4 heterostructure and the surface plasmon resonance of the photoreduced Ag0 together contributed to the improvement of the separation efficiency of photogenerated electrons and holes. In addition, MIP provides the specific recognition ability to preferentially adsorb the target pollutant. The selectivity of photocatalysis was evaluated by the degradation of oxytetracycline and tetracycline solutions. Photoluminescence and transient photocurrent measurements further prove the improved charge separation efficiency of MIP. A plausible photocatalytic reaction mechanism is proposed based on electron spin resonance measurement and the active species trapping experiments, where indicates that the main active species of this photocatalytic process are O2− and h+. This research provides an effective strategy for the simultaneous enhancement of selectivity and activity via molecular imprinting.

Ultrafast Photoinduced Charge Separation in Wide-Band Capturing, Bis-Styryl Bodipy-Fullerene Donor – Acceptor Assemblies

A series of supramolecular donor-acceptor systems capable of wide-band capture and exhibiting photoinduced charge separation were synthesized, and characterized using various techniques as artificial photosynthetic mimics. Both covalent and noncovalent approaches were developed. In the noncovalent approach, the donor host systems comprise of a 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) containing one crown ether entity at the meso-position and two styryl linkers carrying two electron rich triphenylamine (TPA) or phenothiazine (PTZ) entities. The acceptor host system was a fulleropyrrolidine comprised of mono/bis-alkyl ammonium cation(s). In the second approach of covalent bonding, BODIPY was functionalized with two styryl entities carrying TPA or PTZ as additional donors. Additionally, an electron acceptor, fulleropyrrolidine was connected at the meso-position of the BODIPY ring. Owing to the presence of extended conjugation and multiple chromophore entities, the BODIPY host revealed absorbance and emission well into the near-IR region covering the 300–850 nm spectral range. Using redox, computational, absorbance and emission data, energy level diagrams were constructed to help envision the different photochemical events. Spectral evidence for photoinduced charge separation in these systems was established from femtosecond and nanosecond transient absorption studies. The measured rate constants indicated fast charge separation and relatively slow charge recombination revealing their usefulness in light energy harvesting and optoelectronic device building applications.

Charge Generation in Monolayer Transition Metal Dichalcogenides

At the monolayer level, many layered 2D transition metal dichalcogenides (TMDCs) are direct bandgap semiconductors in which photo-excitation creates strongly bound excitons. To incorporate these excitonic semiconductors into solar energy harvesting and conversion devices, it is critical to dissociate excitons to produce long-lived free charge carriers. There are still many open questions regarding the fundamental steps of exciton dissociation and subsequent recombination of charge carriers within 2D TMDCs. These include the roles of defects and traps in localizing charges, the types of interfaces that facilitate fast charge separation and slow recombination, and the role of charge diffusion/delocalization in overcoming the Coulomb binding energy following charge separation. In this talk, I will discuss our efforts at answering some of these questions using a number of 2D TMDC model systems and interfaces. We observe long-lived charge generation in certain neat 2D TMDCs that can be related to specific growth-related defects. Charge generation can also be enhanced by creating interfaces with the appropriate energetics for separating electrons and holes, and the lifetime of the charge-separated state is tied to the degree to which the carrier(s) can escape the interface through diffusion and/or delocalization. These studies provide insight into harnessing the potential of monolayer 2D TMDCs in solar energy harvesting and solar fuels applications.

Collectively Exhaustive Electrodes Based on Covalent Organic Framework and Antagonistic Co‐Doping for Electroactive Ionic Artificial Muscles

AbstractIn this study, high‐performance ionic soft actuators are developed for the first time using collectively exhaustive boron and sulfur co‐doped porous carbon electrodes (BS‐COF‐Cs), derived from thiophene‐based boronate‐linked covalent organic framework (T‐COF) as a template. The one‐electron deficiency of boron compared to carbon leads to the generation of hole charge carriers, while sulfur, owing to its high electron density, creates electron carriers in BS‐COF‐C electrodes. This antagonistic functionality of BS‐COF‐C electrodes assists the charge‐transfer rate, leading to fast charge separation in the developed ionic soft actuator under alternating current input signals. Furthermore, the hierarchical porosity, high surface area, and synergistic effect of co‐doping of the BS‐COF‐Cs play crucial roles in offering effective interaction of BS‐COF‐Cs with poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), leading to the generation of high electro‐chemo‐mechanical performance of the corresponding composite electrodes. Finally, the developed ionic soft actuator based on the BS‐COF‐C electrode exhibits large bending strain (0.62%), excellent durability (90% retention for 6 hours under operation), and 2.7 times higher bending displacement than PEDOT:PSS under extremely low harmonic input of 0.5 V. This study reveals that the antagonistic functionality of heteroatom co‐doped electrodes plays a crucial role in accelerating the actuation performance of ionic artificial muscles.