Charge Transfer Pathway Research Articles

Regulating Charge Transfer in a Heterojunction Photoanode for Efficient Photo‐Charging of Zn‐Air/Sulfion Hybrid Batteries

AbstractIntegrating sulfion‐rich wastewater purification with photo‐charging Zn‐Air batteries enables dual benefits for solar energy storage and environmental protection. However, photo‐charging efficiency is hindered by charge transfer issues. Here, the study synthesizes a CdS@CdIn2S4 core–shell photoelectrode and uses Kelvin Probe Force Microscopy (KPFM) to probe surface potential changes and photo‐charge transfer under illumination. The outer shell (CdIn2S4) exhibits upward band bending and a Conduction Band (CB) more negative than bulk CdS, leading to the accumulation of photoelectrons on the surface, which is detrimental to sulfion oxidation. Vacancy engineering aligns the Fermi energy of two materials, creating an optimal type‐II configuration that accumulates holes on the surface, thereby boosting the photo‐charging current density in Zn‐Air/Sulfion hybrid batteries by 18‐fold. A benchmark photo‐charging current density of 1.26 mA cm−2 is therefore achieved for Zn‐Air/Sulfion hybrid batteries. This work demonstrates the effectiveness of regulating charge transfer pathways in photo‐charging Zn‐Air/Sulfion hybrid batteries, showing potential applications in various photo‐assisted batteries.

Rationally Designed Binder with Polysulfide-Affinitive Moieties and Robust Network Structures for Improved Polysulfide Trapping and Structural Stability of Sulfur Cathode.

Lithium-sulfur batteries (LSBs) have emerged as a promising next-generation energy storage application owing to their high specific capacity and energy density. However, inherent insulating property of sulfur, along with its significant volume expansion during cycling, and shuttling behavior of lithium-polysulfides (LiPSs), hinder their practical application. To overcome these issues, a crosslinked cationic waterborne polyurethane (CCWPU) is rationally designed as a binder for LSBs. The mechanical robustness of CCWPU enables it to withstand the high stress derived from volume expansion of sulfur, facilitating charge-transferring through conserved charge-transfer pathway and promoting interconversion of LiPSs. Additionally, polar urethane groups offer favorable interaction sites with LiPSs, mitigating shuttling behavior of LiPSs via polar-polar interaction. Density functional theory investigations further elucidate that the incorporation of cationic moieties enhances LiPSs immobilization by confining Sn x- (x = 1 or 2) in LiPSs, thereby improving sulfur utilization. Benefiting from these, the cell with CCWPU demonstrates reduced polarization, superior LiPSs conversion rates, and stable cycling performance. Moreover, water-processable nature of CCWPU aligns with environmental consciousness. These diverse functionalities of CCWPU provide valuable insights for the development of advanced binder for LSBs, ultimately improving the electrochemical performances of LSBs.

Metal-organic framework/layered double hydroxide (MOF/LDH) hetero-nanosheet array for capacitive deionization

Achieving rational and precise tuning of the structure and composition of electrode materials represents a promising strategy for enhancing the performance of capacitive deionization (CDI). However, this endeavor encounters significant challenges. Herein, we present an elaborately designed hierarchical porous MOF/LDH Hetero-Nanosheet array (NiCoMn-HNA) which could be used as anode for the efficient Cl− capture. The unique hierarchical and permeable configuration of NiCoMn-HNA offers extensive accessibility to active sites and facilitates rapid electrolyte diffusion, thereby establishing a convenient pathway for efficient charge and ion transfer. Consequently, this enhances both the overall efficiency and respective rates. Furthermore, the synergistic effect between NiCo-ZIF-L and NiCoMn-LDH hollow pseudocapacitive materials significantly contributes to the enhancement of both electrochemical performance and desalination capabilities in NiCoMn-HNA. Accordingly, the NiCoMn-HNA electrode demonstrated larger electrochemical capacitym outstanding salt adsorption capacity (103.1 mg g−1), and remarkable cyclic desalination stability (90.47 % retention rate). Density functional theory (DFT) calculations confirmed that the hollow structure of NiCoMn-HNA promotes efficient the interfacial charge transfer from NiCo-ZIF-L and NiCoMn-LDH, leading to enhanced ion transfer rate and decreased energy required for ion migration. This research introduces a novel strategy for the purposeful design of high-performance electrode materials to advance CDI technology.

Conjugated carbon network mediated - Graphdiyne based Cu2MoS4 homojunction for enhanced charge transfer dynamics

The preparation of stable and environment-friendly catalysts with high photocatalytic performance is of practical significance for the application of photocatalytic hydrogen evolution technology. Graphdiyne has a unique sp and sp2 hybrid structure, making it a potential photocatalyst due to its high surface carrier mobility and porous network structure. In this study, a Cu2MoS4 homojunction composite catalyst with conjugated carbon networks as electron transport channels was prepared by in situ solvothermal growth. Graphdiyne provides an additional pathway for photogenerated electron transfer, improving the efficiency of the interface charge separation. Simultaneously, the built-in electric field at the interface of Cu2MoS4 provides a strong driving force for electron transfer. Owing to the significant visible light absorption and effective multichannel transmission of photogenerated electrons, the Cu2MoS4/graphdiyne composite catalyst exhibited astonishing photocatalytic hydrogen evolution activity (11000 μmol g-1), which is 10 times that of Cu2MoS4 homojunction. Further experimental research and theoretical calculations provided effective evidence for the charge transfer pathway. This work provides a new strategy for constructing efficient hydrogen evolution photocatalysts and regulating the migration of photogenerated electrons.

Boosting charge transfer of BiOBr/AgBr S-scheme heterojunctions via interface Br atom co-sharing for enhanced visible-light photocatalytic activity

Efficient interfacial charge transfer and robust interfacial interactions are crucial for achieving the superior spatial separation of carriers and developing efficient heterojunction photocatalysts. Herein, BiOBr/AgBr S-scheme heterojunctions are synthesized via the co-sharing of Br atoms using an ion-exchange approach, which involves the in-situ growth of AgBr nanoparticles on the surfaces of BiOBr nanosheets. It is revealed that successful construction of a high–quality interface with strong interactions via Br atom bridge between BiOBr and AgBr, which provided a rapid migration channel for charge carriers. In addition, in-situ XPS, Kelvin probe force microscopy, and electron spin resonance evaluations confirmed the establishment of an S-scheme charge-transfer pathway in this tightly contacted heterojunction, which could efficiently prevent the recombination of photogenerated carriers while retaining carriers with a high redox capacity. Finally, the photocatalytic test confirmed that the BiOBr/AgBr heterojunction showed excellent photocatalytic performance and wide applicability thanks to the construction of high quality heterojunction. Overall, this work highlights the importance of rational design of heterogeneous interfaces at the atomic level in photocatalysis, and contributes to rationally design BiOBr-based S-scheme heterojunctions photocatalytic materials with high quality atomic co-sharing interfaces.

Efficient Charge Transfer Driven Electrochemiluminescence in Heteroatom-Involved Cocrystal Engineering for Detection of Uranyl Ions.

Embracing strategies that circumvent the complexities and disordered structures of electrochemiluminescence (ECL) emitters to improve charge transfer efficiency is crucial for advancing ECL technology to the forefront. Here, heteroatom-involved cocrystal engineering was introduced, constructing an ECL system with controllability of the charge transfer process. Through the mutual recognition and coassembly between functional monomers, highly ordered cocrystal superstructures are formed. The layered donor-acceptor arrays in cocrystals accelerated charge transfer, producing a remarkable ECL performance. Furthermore, distinct heteroatoms possess the capability to modulate the charge distribution of monomers by either pushing or pulling electrons. This modulation ultimately affects the charge transfer pathways within cocrystals, enabling ECL emissions of varying intensities and wavelengths. Notably, the presence of UO22+ would significantly inhibit the charge transfer in cocrystals, causing a quenching of ECL signal. This unique characteristic enables precise and selective detection of UO22+. The heteroatom-involved cocrystals hold immense potential to construct next-generation ECL emitters and create fresh opportunities for the advancement of ECL technology.

Plasma-assisted construction of waterfall-type IEF in N-TiO2/WO3 S-scheme heterojunction for efficient visible-light-driven degradation of Cl-VOCs

Constructing S-scheme heterojunctions with a robust internal electric field (IEF) to enhance the photocatalytic degradation of chlorinated volatile organic compounds (Cl-VOCs) presents a significant challenge. Herein, an innovative S-scheme heterojunction of N-doped titanium dioxide (TiO2) and tungsten trioxide (WO3) with abundant oxygen vacancies (OVs) was synthesized and manipulated for the first time via an eco-friendly two-step plasma. The charge transfer pathway between TiO2 and WO3 was analyzed using UV–Vis DRS, XPS, UPS, and EPR measurements, confirming the successful formation of the S-scheme heterojunction. Interestingly, two novel types of IEF, stream-type and waterfall-type were proposed for the first time to distinguish the IEF strength before and after regulation. Under visible light, 5NTW, with the optimal ratio of 4.66 at% nitrogen and 5 wt% WO3, achieved the highest degradation efficiency and carbon dioxide mineralization rate, 95.4% and 94.1% for chlorobenzene, respectively. The performance enhancement was attributed to the fact that N-doping modifies the electronic structure and work function of TiO2, enhancing the Fermi level difference (ΔEf) with WO3. Meanwhile, the plasma treatment roughened the surface topography of the catalyst and increased the content of OVs, which serve as charge traps and bolster active sites. These synergies led to a transformation from a stream-type IEF of TW to a waterfall-type IEF of 5NTW. KPFM, zeta potential tests, and DFT calculations confirmed that the IEF strength and the number of electron transfers in the waterfall-type IEF are 3.17 and 2.04 times greater, respectively, than those in the stream-type IEF. This strategy transcends the limitations of previous work, offering a novel perspective on the integrated optimization of photocatalysts for superior performance and also further broadens the application prospects of nonthermal plasma technology.

Pseudo Molecular Doping and Ambipolarity Tuning in Si Junctionless Nanowire Transistors Using Gaseous Nitrogen Dioxide

AbstractAmbipolar transistors facilitate concurrent transport of both positive (holes) and negative (electrons) charge carriers in the semiconducting channel. Effective manipulation of conduction symmetry and electrical characteristics in ambipolar silicon junctionless nanowire transistors (Si‐JNTs) is demonstrated using gaseous nitrogen dioxide (NO2). This involves a dual reaction in both p‐ and n‐type conduction, resulting in a significant decrease in the current in n‐conduction mode and an increase in the p‐conduction mode upon NO2 exposure. Various Si‐JNT parameters, including “on”‐current (Ion), threshold voltage (Vth), and mobility (µ) exhibit dynamic changes in both the p‐ and n‐conduction modes of the ambipolar transistor upon interaction with NO2 (concentration between 2.5 – 50 ppm). Additionally, NO2 exposure to Si‐JNTs with different surface morphologies, that is, unpassivated Si‐JNTs with a native oxide or with a thermally grown oxide (10 nm), show distinct influences on Ion, Vth, and µ, highlighting the effect of surface oxide on NO2‐mediated charge transfer. Interaction with NO2 alters the carrier concentration in the JNT channel, with NO2 acting as an electron acceptor and inducing holes, as supported by Density Functional Theory (DFT) calculations, providing a pathway for charge transfer and “pseudo” molecular doping in ambipolar Si‐JNTs.

Confined growth of Cu2O quantum dots on oxygen vacancies mediated Bi24O31Br10 nanosheets for efficient tetracycline hydrochloride photodegradation driving by S-scheme mechanism

The rational design of the photocatalytic system with high charge separation efficiency is essential to the photocatalytic process. In this work, the oxygen vacancies mediated Cu2O quantum dots/Bi24O31Br10 nanosheets heterojunctions were constructed, where the concentration of oxygen vacancies was increased with the increasing amount of Cu2O. The optimized Cu2O/Bi24O31Br10 nanocomposites exhibited significantly enhanced apparent kinetic constant values toward tetracycline hydrochloride (TCH) photodegradation, showing an increase of 5.3 times compared to bare Cu2O and 2.2 times compared to pure Bi24O31Br10. By taking advantage of the inherent electronic field generated at the interface, there is a significant enhancement in charge separation efficiency, leading to an improvement in photocatalytic performance. Furthermore, a comprehensive investigation was conducted to determine the various factors that impact the efficiency of TCH removal. These factors encompassed the catalyst dosage, TCH concentration, pH level, and presence of anions. Based on the in-situ X-ray photoelectron spectroscopy (XPS), reactive oxygen species detection, as well as density functional theory calculation (DFT), the S-scheme charge transfer pathway was verified. This work contributes to the design of p-n S-scheme heterojunctions for environmental remediation.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B-N Lewis Pairs for Visible-Light Photocatalysis.

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far-reaching in facilitating photocatalysis. A series of B-N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B-N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free-charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.

Prolonging Charge Carrier Lifetime via Intraband Defect Levels in S-Scheme Heterojunctions for Artificial Photosynthesis.

S-scheme heterostructure photocatalysts, distinguished by unique charge-transfer pathways and exceptional catalytic redox capabilities, have found widespread applications in addressing challenging chemical processes, including the photocatalytic reduction of CO2 with a high reaction barrier. Nevertheless, the influence of intraband defect levels within S-scheme heterojunctions on charge separation, carrier lifetime, and surface catalytic reactions has, for the most part, been overlooked. Herein, we develop a tunable defect-level-assisted strategy to construct an electron reservoir, effectively prolonging the lifetime of charge carriers through the rapid capture and gradual release of photoelectrons within WO3-x/In2S3 S-scheme heterojunctions, as authenticated by femtosecond transient absorption spectroscopy and theoretical simulations. The surface photoredox mechanism, unraveled by Gibbs free energy calculations, demonstrates that oxygen-vacancy-induced defect states in WO3-x/In2S3 heterojunctions unlock the rate-determining H2O oxidation into free oxygen molecules by forming metastable oxygen intermediates, contributing to the facilitation of H2O photooxidation. This distinct role, combined with the extended carrier lifetime, results in boosted CO2 photoreduction with nearly 100 % CO selectivity in the absence of any photosensitizer or scavenger. Our work sheds light on the role of controllable defect levels in governing charge transfer dynamics within S-scheme heterojunctions, thereby inspiring the development of more advanced photocatalysts for artificial photosynthesis.

Rational design of MoS2/CNT heterostructure with rich S-vacancy for enhanced HER performance.

Molybdenum disulfide (MoS2) is a promising electrocatalyst for the hydrogen evolution reaction (HER) due to excellent stability and low cost. However, the utilization in electrocatalytic hydrogen evolution is constrained by inherent shortcomings, including fewer edge active sites, poor dispersion, and electrical conductivity. In this work, MoS2 was compounded with carbon nanotubes (CNTs), which are known for their high specific surface area and excellent electrical conductivity. These CNTs, laden with oxygen-containing functional groups, provided nucleation sites that facilitated the rapid assembly of MoS2 nanoflowers under hydrothermal conditions within 3h. Due to their diminutive size (∼300nm), these nanoflowers possess a large specific surface area and numerous active sites at their edges. Furthermore, MoS2 nanoflowers exhibited a high concentration of intrinsic S-vacancies. This heterojunction material exhibited superior HER properties. In addition, density functional theory simulation further confirmed that the MoS2 with S vacancy and CNT heterojunction electrocatalysts (VS-M/C) provided a fast charge transfer pathway for water electrolysis, and analysis showed that the conduction band minimum and valence band maximum were mainly contributed by the d orbits of Mo and the p orbits of C. This study proffered a novel approach for the engineering of high-performance MoS2-based HER electrocatalysts.

Accelerated Ion-Electron Transport in Bi-Heterostructures Constructed Based on Ohmic Contacts for Efficient Bi-Directional Catalysis of Lithium-Sulfur Batteries.

Although lithium-sulfur batteries have satisfactory theoretical specific capacity and energy density, they are difficult to further commercialize due to the shuttle effect of soluble polysulfides and slow sulfur oxidation kinetics. Based on this, in this work, the catalyst MXene-VS4-SnS2 (MVS), a dual heterostructured catalyst with ohmic contacts, is prepared by a one-step hydrothermal method and electrostatic self-adsorption for lithium-sulfur battery cathode materials. Experimental and theoretical results show that the ohmic contact induces spontaneous charge rearrangement, resulting in the formation of a fast charge transfer pathway at the MVS heterojunction interface, which helps to reduce the energy barrier for polysulfide reduction and Li2S oxidation during the discharge/charge process. In addition, the inherent sulfophilicity of VS4 and SnS2 promotes the conversion of S species, while the pleated MXene nanosheets not only provide a highly conductive network for the active sulfur but also retain a rich internal space to maintain the integrity of the cathode structure during the continuous cycling process. As a result, the MVS cathode exhibits excellent electrochemical performance even under high sulfur loading. The integration of excellent performance with a facile synthesis process provides a promising approach for designing highly efficient electrocatalysts suitable for the energy field.

Fabrication and Mechanism Insight of Multidimensional Coupled Metal-Free van der Waals Heterostructures for Enhanced Photocatalytic Hydrogen Evolution.

It is an arduous issue to significantly improve the charge separation efficiency of polymer photocatalysts due to their inherently high exciton binding energy. Herein, based on an interfacial coupling and atom diffusion strategy, a metal-free 3D/2D van der Waals (VdW) heterojunction is fabricated through the modification of rich-vacancy wrinkle-like S8 (Vs-S8) microspheres on the surface of S-doped polymeric carbon nitride (S-PCN) nanosheets. The insight into the mechanism reveals that the interfacial coupling effect induces a strong built-in electric field from S-PCN to Vs-S8, and the carrier transfer behavior abides by the type-II charge transfer pathway, thereby dramatically improving the separation efficiency and transport kinetics of photogenerated carriers. As a result, the as-prepared metal-free 3D/2D Vs-S8/S-PCN VdW heterojunction is endowed with more superior photocatalytic hydrogen evolution (PHE) performance than PCN. The highest average PHE rate is about 11.3 times higher than that of PCN, and the apparent quantum efficiency reaches 30.1% at 400 nm on the optimal 3%-Vs-S8/S-PCN sample. This work contributes a new design strategy for a metal-free VdW heterojunction and provides a feasible avenue for improving the carrier separation efficiency of polymer photocatalysts.

Electrostatic Confinement‐Induced Excited Charge Transfer in Ionic Covalent Organic Framework Promoting CO2 Reduction

We demonstrate an electrostatic confinement‐induced charge transfer pathway in a supramolecular photocatalyst comprising of an ionic covalent organic framework (COF) and cationic metal complexes. The dynamic electrostatic interactions not only attract cations around the COF to accept photogenerated electrons, but also allows for a retention of homogeneous catalytic characters of complexes, making a subtle balance. Accordingly, the electrostatic confinement effect facilitates the forward electron transfer from a photoexcited COF to cationic Co complex, realizing a remarkable photocatalytic CO2 reduction performance. Its catalytic efficiency is far superior to the supramolecular counterparts with Van‐der‐Waals or hydrogen bonding interactions. This work presents an insight for enhancing charge transfer in supramolecular systems, and provides an effective approach for construction of highly efficient photocatalysts.

Convenient synthesis of hollow tubular In2O3/PDA S-scheme inorganic/organic heterojunction photocatalyst for H2O2 production and its mechanism

The development of heterojunction photocatalysts for hydrogen peroxide (H2O2) generation is both environmentally sustainable and cost-effective but presents considerable challenges. In this study, we synthesized hollow tubular indium oxide (In2O3) by calcining In-MIL-68 and subsequently composited it with polydopamine (PDA) via in-situ self-polymerization. This process resulted in the formation of an In2O3/PDA step-scheme (S-scheme) heterojunction. The optimized sample demonstrated H2O2 production rates approximately 2.1 and 4.5 times higher than the pure In2O3 and PDA, respectively. The enhanced photocatalytic performance of the In2O3/PDA composite is the result of several synergistic factors: increased light absorption due to the hollow structure, a larger specific surface area, and high separation efficiency of photo-generated electron-hole pairs facilitated by the S-scheme heterojunction. In-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) confirmed the charge transfer pathway follows the S-scheme mechanism. This work not only highlights a practical method for constructing inorganic/organic S-scheme heterojunction photocatalysts but also provides a detailed analysis of their underlying mechanisms, paving the way for more efficient and sustainable photocatalytic systems.

Z-scheme heterojunction photocatalyst of LaFeO3@CoS for tetracycline hydrochloride degradation by persulfate activation using visible light

An efficient and stable LaFeO3@CoS Z-scheme heterojunction photocatalyst was prepared through the hydrothermal method (HT). Photocatalytic activity of the LaFeO3@CoS was assessed by activating persulfate under visible light for the degradation of tetracycline (0.1 g/L). Under the condition of 0.06 g/L of KHSO5 (Peroxymonosulfate, PMS), the degradation efficiency of 88.7 % was achieved in 40 min using the 0.02 g/L of developed photocatalyst. The degradation kinetic constants of LaFeO3@CoS were 2.79 and 2.23 times higher than those of LaFeO3 and CoS, respectively. Furthermore, the catalyst exhibited excellent stability over five consecutive degradation cycles. Possible degradation mechanisms and the electron transfer mechanism of the heterojunction formed by the LaFeO3@CoS were investigated by quenching experiments, nitrogen N₂ purging experiments, electron spin resonance (ESR) measurements and corresponding electrochemical analyses. In the LaFeO3@CoS/Vis/PMS system, the Z-scheme charge transfer pathway not only accelerated charge transport efficiency but also effectively spatially separated electrons and holes, enhancing the photocatalytic performance of the photocatalyst. Additionally, the generation of reactive species such as 1O2, O2•−, and SO4• − significantly contributed to the improved degradation efficiency of the present catalyst during the degradation process.

Non‐Fused Star‐Shape Giant Trimer Electron Acceptors for Organic Solar Cells with Efficiency over 19 %

AbstractOrganic solar cells (OSCs) based on giant molecular acceptors (GMAs) have attracted extensive attention due to their excellent power conversion efficiency (PCE) and operation stability. However, the large conjugated plane of GMAs poses great challenges in regulating the solubility, over‐size aggregation and yield, which in turn further constrains their development in commercial products. Herein, we employ a non‐fused skeleton strategy to develop novel non‐fused star‐shape trimers (3BTT6F and 3BTT6Cl) for improving device performance. Single‐bond linkage can break the rigid planarity to form a 3D architecture, generating multidimensional charge transfer pathways. Importantly, the non‐fused skeleton strategy can not only significantly improve solubility and synthesis yield, but also effectively suppress molecular excessive aggregation. Consequently, due to the optimized film‐forming process and charge dynamics, 3BTT6F‐based binary device obtains a high PCE of 17.52 %, which is significantly higher than the reported fully fused trimers. Excitingly, 3BTT6F‐based ternary device even obtains a top‐level PCE of 19.26 %. Furthermore, the non‐fused star‐shape configuration also endows these acceptors with enhanced intermolecular interaction in the active layer, demonstrating excellent operational stability. Our work emphasizes the potential of non‐fused star‐shape trimers, providing a new pathway for achieving highly efficient and stable OSCs.

Multifunctional Conductive MOFs Enhance the Photocatalytic Hydrogen Evolution Efficiency of S-Type Ni3(HITP)2/TiO2 Heterojunctions.

Despite their high surface area, remarkable porosity, and efficient charge transfer mechanisms, conductive MOFs have found limited utilization within the domain of photocatalysis. In this study, we synthesized a cutting-edge S-type Ni3(HITP)2/TiO2 heterojunction photocatalyst exhibiting outstanding light harvesting and prolonged lifetime of photogenerated electrons through an in situ synthesis approach. Compared with TiO2, the composite materials not only significantly increase the specific surface area by 4.07 times but also expand the visible light absorption edge from 400 to 1100 nm. The hydrogen production rate of Ti/Ni-3 reached 4.927 mmol·g-1·h-1, which is 4.51 times that of TiO2. The S-type interface charge transfer pathway of the Ni3(HITP)2/TiO2 composite material was inferred by band structure, in situ XPS, SPV, and free radical capture, which improves charge separation and extends the carrier lifetime to undergo directional migration driven by an IEF. This is the main reason for the improved photocatalytic performance of Ni3(HITP)2/TiO2 composite materials.

Regulation of Exciton Effects in Functionalized Conjugated Polymers by B‐N Lewis Pairs for Visible‐Light Photocatalysis

Strong excitonic effects are common in organic conjugated polymer semiconductors, severely hindering the generation of free charge carriers for conducting photocatalysis. Therefore, exploring new channels to modulate exciton dissociation in polymers is far‐reaching in facilitating photocatalysis. A series of B‐N Lewis pair functionalized conjugated polymers have been developed to minimize exciton effects by modulating charge transfer pathways. Theoretical studies have shown that introducing B‐N Lewis pairs can dramatically increase the distance of charge transfer (D index) and the amount of electron transfer and reduce the Coulomb attraction energy (EC), which contributes to breaking the equilibrium of the coexistence of excitons and charge carriers. Further experimental results show that the singlet excitons are efficiently dissociated into more free‐charge carriers under photoexcitation to participate in surface reactions. The optimized polymer PyPBM shows an exponential increase in photocatalytic hydrogen and hydrogen peroxide production performance by visible light illumination.