Field Of Photocatalysis Research Articles

Structural Design on Porous Aromatic Frameworks for Photocatalysis

Photocatalytic technology has shown great potential in various fields such as environmental purification, energy conversion, and chemical transformations due to its green, sustainable, and low‐cost characteristics. Porous aromatic frameworks (PAFs) with high specific surface areas, designable local structures, and abundant active sites could potentially serve as efficient photocatalysts for various catalytic reactions. This makes PAFs have a wide range of application prospects and significant advantages in the field of photocatalysis. This concept discusses the recent progress of photocatalysis over PAFs. Various strategies are used to solve the general problems of photocatalyst, such as poor light absorption, low carrier separation efficiency and poor stability, which further reveal the relationship between their structure and performance.

The application of semiconductor nanomaterials in renewable energy

Abstract. In the development of renewable energy, the usage of solar cells, fuel cells, hydrogen energy, thermoelectric energy, and thermal energy has become a significant focus of research and development. Semiconductor nanomaterials play important roles in these fields. This paper focuses on the usage of TiO2 and In2O3 in renewable energy and finds out the trends and outlook of semiconductor nanomaterials in this field. TiO2 nanomaterials have attracted widespread attention due to their unique structure and excellent properties, such as their large specific surface area, high surface activity, and sensitivity. TiO2 nanomaterials are highly active in photovoltaic applications and play an important role in the search for renewable, clean energy technologies. In2O3 is an excellent n-type transparent semiconductor functional material, characterized by high sensitivity, low resistivity, good conductivity, high catalytic activity, and wide bandgap width. It has shown good competitiveness in gas sensors, solar cells, and photocatalysis fields. Although these semiconductor nanomaterials have many advantages, there are still some drawbacks that hinder their development. There is still much work to be done for the wider application of semiconductor nanomaterials in the field of renewable energy.

DFT-Based Mechanistic Exploration and Application in Photocatalytic Heterojunctions.

Density functional theory (DFT) is one of the most widely used methods in the field of computational materials and has become an important research method for photocatalytic heterojunctions. Based on the research progress of DFT in the field of photocatalytic heterojunctions, this review introduces three kinds of heterojunction modeling in detail as well as the problems encountered in the construction process and the solutions. It provides a comprehensive review of the calculation methods of important parameters related to photocatalytic heterojunctions. Comparison, analysis, and discussion were conducted on some functional selections and calculation results based on experimental data. Finally, the limitations and shortcomings of DFT in the field of photocatalytic heterojunctions are pointed out. This review will provide valuable guidance for the calculation and analysis of the performance of photocatalytic heterojunctions and help promote the wider application of DFT in the field of photocatalysis.

One-step fabrication of Bi2MoO6 nanowires-g-C3N4 composites for outstanding photocatalytic performance in cyclohexane oxidation

Selective oxidation of cyclohexane into cyclohexanone (K) and cyclohexanol (A) stands as a pivotal process in industrial chemistry. However, the challenges associated with activating the C-H bond and the vulnerability of KA oil to over-oxidation detract from the economic significance of this reaction. This study focuses on the preparation of a bismuth molybdate ultrathin nanowires-carbon nitride (Bi2MoO6-g-C3N4) heterojunction through a one-step hydrothermal approach for significantly improving the photocatalytic oxidation of cyclohexane. Bi2MoO6 ultrafine nanowires with the diameter of 6 nm were adhered tightly on the surface of g-C3N4 nanosheets with the assistance of oleyl amine. The type II heterojunction of Bi2MoO6-g-C3N4 composite facilitated a more efficient separation of charges and boosted the photocatalytic performance in the cyclohexane oxidation. The Bi2MoO6-g-C3N4 composite demonstrated outstanding photocatalytic performance with a 10.66 % conversion rate of cyclohexane, surpassing the individual efficiencies of Bi2MoO6 and g-C3N4 by 1.9 and 2.2 times, respectively. Moreover, it demonstrated an outstanding KA oil selectivity of 99.32 %, showcasing exceptional levels of both conversion and selectivity simultaneously. Through the utilization of photoelectrochemical analysis, research on band structures, experiments on radical trapping and monitoring, we have extensively investigated the mechanism of photocatalysis. The type II charge transfer in Bi2MoO6-g-C3N4 heterojunction restricted the redox capacity of electrons in the conduction band and holes in the valence band, effectively curbing over-oxidation reactions of KA oil, thus achieving remarkable KA oil selectivity. It offers a valuable insight into the creation of heterojunctions to boost the efficiency of photocatalytic oxidation of cyclohexane, showing promise for advancing the field of photocatalysis.

Fabrication of core–shell nanostructure via novel ligand-defect reassembly strategy for efficient photocatalytic hydrogen evolution and NO removal

The core–shell structure often exhibits unique properties, resulting in superior physical and chemical performance distinct from individual component in the field of photocatalysis. However, traditional prepared methods such as template synthesis and layer-by-layer self-assembly are relatively complex. Therefore, it is necessary to explore an efficient and expedient approach. Here, we have proposed a convenient method to gradually destroy the terephthalic acid (BDC) of MIL-125 from the outer to inner layers through hydrothermal stirring, followed by reassembling with photosensitive 2-amino-terephthalic acid (BDC-NH2) into the exposed Ti-oxo clusters left by the BDC to create photocatalysts featuring a core–shell configuration. The special core–shell sample with the analogous mixture of MIL-125 and MIL-125-NH2 function as a high-performance dual-functional photocatalyst for hydrogen generation and NO elimination. The optimal core–shell material (M-125-45-N) exhibits an outstanding photocatalytic hydrogen production rate of 3.74 mmol·g−1·h−1 and an excellent photocatalytic NO removal rate of 70.15 %. The apparent quantum yield (AQY) value and solar-to-hydrogen energy conversion efficiency (STH) at specific wavelengths are also investigated. The Density functional theory (DFT) calculation, In-situ Fourier transform infrared (In-situ FT-IR) and Electron spin resonance (ESR) have suggested that the enhanced photocatalytic activity of optimal core–shell material arised from its stronger adsorption capacity towards reactants, promoting the production of reactive oxygen species (ROS) conducive to photocatalytic reactions. This study represents the first investigation of a dual functional core–shell MOFs formed via ligand-defect reassembly, showcasing the excellent efficacy in photocatalytic hydrogen evolution and NO removal, which contributes to the feasible development of novel dual-functional photocatalysts with core–shell structures.

Theoretical design of Z-scheme photocatalyst for water splitting with excellent catalytic performance: GeSe/PtS2 heterojunction

In the face of the urgent need for energy transition, Z-scheme heterojunctions are considered highly suitable candidates for future photocatalytic applications, owing to their exceptional optoelectronic characteristics and high catalytic efficiency. This paper systematically investigates the geometric structure, optoelectronic properties, and catalytic efficiency of the GeSe/PtS2 heterojunction through detailed first-principles calculations. The findings indicate that the band structure of the GeSe/PtS2 heterojunction presents a staggered Type-Ⅱ band alignment and exhibits an indirect band gap measuring 1.75 eV. Charge transfer analysis reveals that under the interplay of an intrinsic electric field directed from GeSe to PtS2 and the band bending occurring at the heterojunction interface, the GeSe/PtS2 heterojunction conforms to the obvious Z-scheme electron transfer mechanism characteristics. This facilitates the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) to proceed smoothly on opposite sides of the heterojunction. Across the pH range of 0 to 14, the heterojunction's band edge positions successfully span the redox potentials of water, and can still meet the hydrolysis potential requirements under strain. In addition, the GeSe/PtS2 heterojunction not only effectively compensates for the poor absorption of PtS2 monolayer to visible light, but also achieves a wider visible light absorption range through the strain-induced redshift in the spectrum. At the same time, the solar to hydrogen (STH) efficiency of up to 15.56% further underscores the substantial catalytic potential of the GeSe/PtS2 heterojunction, offering promising design strategies for a technological revolution in the field of photocatalysis.

Boosted Photocatalytic CO2 Conversion of a Cs2AgBiBr6@Co3O4 Composite with High Activity and Selectivity under Low-Concentration CO2 and Natural Sunlight

To explore high-efficiency photocatalysts that can operate under low-concentration CO2 and natural light conditions remains a significant challenge in the field of photocatalysis. Here, we have constructed lead-free Cs2AgBiBr6@Co3O4 (CABB@Co3O4) composites with compact heterogenous interfaces, enhanced CO2 adsorption capability and excellent photoelectronic characteristics. The optimal CABB@Co3O4 heterojunction exhibits nearly 100% selectivity for visible-light-driven CO2 to CO conversion with the high catalytic efficiency and stability in high-purity and diluted CO2. Importantly, the CABB@Co3O4 photocatalyst is one of a few examples to drive photocatalytic CO2 reduction under the 5v% CO2 and natural sunlight, exhibiting a linear relationship between CO evolution rate and light intensity. The outstanding photocatalytic performance mainly originates from the suppressed carrier recombination and the decreased energy barrier for the formation of the key *COOH intermediate. This work provides prospective guidance for designing efficient photocatalysts toward CO2 conversion under the actual environmental conditions.

Graphitic Carbon Nitride Based Semiconductors and Their Applications in the Field of Photocatalysis

An increasing number of advanced semiconductor materials have been reported with the progress of theoretical and practical researches. The graphitic carbon nitride (g-C3N4) stands out as a highly promising semiconductor photocatalyst. It is known for its visible-light reaction and good chemical stability, indicating its potential for extensive use in photocatalysis. Recently, rapid progress has been made in researching g-C3N4-based semiconductor substances in photocatalysis. Till now, a large amount of work has focused on the applications of g-C3N4 in photocatalysis. This work focuses on those researches concerning with g-C3N4-based photocatalytic substances. Their structural characteristics, synthesis techniques, and efficiency enhancement are discussed in detail. Besides, their applications in different photocatalytic reactions are also highlighted. These reactions include hydrogen production by water decomposition, degradation of organic matter, carbon dioxide reduction, and photocatalytic bactericide. This article also points out the problems and challenges in the photocatalytic performance. Meanwhile, the stability of g-C3N4 is also highlighted. It also puts forward the promising research directions of g-C3N4 in the field of photocatalysis.

A novel bi-level optimal strategy-assisted design boosting discovery of specific surface area of perovskite oxide for effective photocatalysis

Due to the inherent property of materials, photocatalysis plays a crucial role in diverse applications, such as the degradation of organic pollutants, fuel production, and nitrogen fixation. Perovskites, in particular, are remarkable for their high light absorption rate and energy conversion efficiency within the visible light range, thereby positioning them as promising photocatalysts. Given that specific surface area (SSA) is a critical metric for evaluating photocatalytic performance, accurately and quickly predicting the SSA of perovskites has emerged as a key area of technical research. Therefore, it is essential to explore the relationship between potential materials descriptors and SSA, which can significantly expedite the discovery of photocatalyzed perovskite materials with high SSA. In this study, we proposed a bi-level optimization method that combines descriptors identified strategy and model optimization strategy for predicting the SSA of unknown perovskite candidates, thereby elucidating the relationship between material features and SSA. Initially, at the upper level, the Gradient Boosting Regression combined with Recursive Feature Elimination (RFE-GBR) method was employed to identify crucial features that are closely correlated with the SSA of photocatalyzed perovskites. Subsequently, the Sure Independence Screening.Sparsifying Operator (SISSO) was utilized to develop new descriptors that exhibited strong correlations with SSA. Based on refined descriptors identifiied at the upper level, at the lower level, the optimal model strategy was obtained by Improved Osprey Optimization Algorithm (IOOA) using golden sine strategy and Gradient Boosting Regression (GBR) regression to tune the key parameters of GBR for optimizing SSA. The optimal designing method achieved remarkable predictive performance with R2 (R-squared) score of 0.90 and MAE (Mean Absolute Error) of 3.97 m2/g, along with 5-fold cross-validation. Then this method was applied to predict the SSA of 300 unidentified ABO3 perovskites. Comparison with experimental data revealed that our approach significantly accelerated the development of perovskite materials with superior photocatalytic properties, showing the potential of our model in advancing the field of photocatalysis.

Role of Morphology on Zinc Oxide Nanostructures for Efficient Photoelectrochemical Activity and Hydrogen Production.

Energy generation today heavily relies on the field of photocatalysis, with many conventional energy generation strategies now superseded by the conversion of solar energy into chemical or thermal energy for a variety of energy-related applications. Global warming has pointed to the urgent necessity of moving away from non-renewable energy sources, with a resulting emphasis on creating the best photocatalysts for effective solar conversion by investigating a variety of material systems and material combinations. The present study explores the influence of morphological changes on the photoelectrochemical activity of zinc oxide nanostructures by exploiting electrodeposition and capping agents to control the growth rates of different ZnO facets and obtain well-defined nanostructures and orientations. A zinc nitrate (Zn (NO3)2) bath was used to electrodeposit ZnO nanostructures on an indium tin oxide glass (ITO) substrate at 70 °C with an applied potential of -1.0 V. Ethylenediamine (EDA) or ammonium fluoride (NH4F) were added as capping agents to the zinc nitrate bath. Extensive evaluation and characterization of the photoelectrochemical (PEC) capabilities of the resulting morphology-controlled zinc oxide nanostructures confirmed that altering the ZnO morphology can have positive impacts on PEC properties.

Highly active Cu2O/CoCo-PBA S-scheme heterojunction for enhanced visible-light-driven hydrogen evolution

Prussian blue analogues is a unique class of organic-inorganic hybrid materials that have garnered significant attention in the field of photocatalysis due to their large specific surface area and abundant active sites. However, their potential is limited by the challenge of photogenerated charge carrier recombination. To address this issue, we successfully synthesized a tightly coupled Cu2O/CoCo-PBA S-scheme heterojunction catalyst using ultrasound-assisted and thermal treatment methods, aiming to reduce the recombination of photogenerated charge carriers. In this system, CoCo-PBA serves as the electron donor, while Cu2O acts as the electron acceptor. The closely coupled interface between these materials shortens the electron transfer distance. Under 10 W white light irradiation, the Cu2O/CoCo-PBA composite photocatalyst demonstrated remarkable hydrogen evolution activity, with a hydrogen production rate of 5.98 mmol⋅g⁻¹⋅h⁻¹, which is 6.4 times that of CoCo-PBA alone. This S-scheme heterojunction strategy lays the groundwork for the design and large-scale application of highly active visible-light-driven photocatalysts.

Preparation and Photocatalytic Performance of In2O3/Bi2WO6 Type II Heterojunction Composite Materials.

Bismuth-based photocatalytic materials have been widely used in the field of photocatalysis in recent years due to their unique layered structure. However, single bismuth-based photocatalytic materials are greatly limited in their photocatalytic performance due to their poor response to visible light and easy recombination of photogenerated charges. At present, constructing semiconductor heterojunctions is an effective modification method that improves quantum efficiency by promoting the separation of photogenerated electrons and holes. In this study, the successful preparation of an In2O3/Bi2WO6 (In2O3/BWO) II-type semiconductor heterojunction composite material was achieved. XRD characterization was performed to conduct a phase analysis of the samples, SEM and TEM characterization for a morphology analysis of the samples, and DRS and XPS testing for optical property and elemental valence state analyses of the samples. In the II-type semiconductor junction system, photogenerated electrons (e-) on the In2O3 conduction band (CB) migrate to the BWO CB, while holes (h+) on the BWO valence band (VB) transfer to the In2O3 VB, promoting the separation of photoinduced charges, raising the quantum efficiency. When the molar ratio of In2O3/BWO is 2:6, the photocatalytic degradation degree of rhodamine B (RhB) is 59.4% (44.0% for BWO) after 60 min illumination, showing the best photocatalytic activity. After four cycles, the degradation degree of the sample was 54.3%, which is 91.4% of that of the first photocatalytic degradation experiment, indicating that the sample has good reusability. The XRD results of 2:6 In2O3/BWO before and after the cyclic experiments show that the positions and intensities of its diffraction peaks did not change significantly, indicating excellent structural stability. The active species experiment results imply that h+ is the primary species. Additionally, this study proposes a mechanism for the separation, migration, and photocatalysis of photoinduced charges in II-type semiconductor junctions.

Low-temperature hydrothermal self-assembly synthesis of ZnIn2S4/chitosan-graphene aerogels for enhanced aqueous pollutants removal

A novel visible-light-responsive ZnIn2S4/chitosan graphene aerogel (ZCGA) was prepared using a low-temperature hydrothermal self-assembly method for the adsorption and degradation of tetracycline. Infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) indicated interactions between ZnIn2S4 and chitosan graphene aerogel (CGA). Under the irradiation of a 500 W xenon lamp, ZCGA exhibited excellent adsorption and photocatalytic degradation performance for tetracycline, with a removal rate exceeding 90 % within 180 min. This significant performance improvement is attributed to the high carrier transport properties of CGA, which greatly enhanced the activity of the photocatalytic reaction and also showed high efficiency in removing other types of organic pollutants. Radical trapping experiments further confirmed that the superoxide anion (·O2−) is the main active species in the photocatalytic process. In addition, the monolithic aerogel has good recyclability and mechanical stability. This study not only demonstrates the great potential of ZCGA in the field of photocatalysis but also provides new ideas for designing efficient, recyclable, and visible light-responsive photocatalysts.

Application of MOFs in the Field of Photocatalysis

MOFs is the abbreviation of Metal organic Framework. Compared with the traditional inorganic metal materials, MOFs materials have the advantages of larger surface area, more diverse structure and function, and have been widely used in the field of photocatalysis. From the perspective of photocatalysis, this paper summarizes the application research process of MOFs material in the field of photocatalysis in the recent years, including photocatalytic decomposition of water to hydrogen production, photocatalytic decomposition of carbon dioxide, degradation of pollutants and so on. The application prospect of MOFs materials is prospected.

Electronic and photocatalytic properties of Cu4 cluster-modified Ag/g-C3N4 single-atom catalysts: A hybrid DFT study

Increasing the active sites on the catalyst surface has been a key goal to increase the catalyst efficiency. This paper presents an efficient conversion of solar energy into chemical energy, realized by a Cu4 cluster-assisted single-atom catalyst (Ag-doped g-C3N4). The catalyst enhances charge transfer and light absorption, and the unique advantages of this approach in the field of photocatalysis are substantiated by density functional theory. Under the synergistic effect of Cu4 clusters, the electronic state density distribution of the Ag single-atom catalyst substrate is drastically altered, which realizes the increase of substrate active sites and rapid charge separation and transfer. Compared with the pristine substrate g-C3N4, the new electronic state distribution and the generation of impurity energy levels lead to the narrowing of the band gap from 2.77 to 1.83 eV, accelerating the transfer and separation of electrons and holes, and enlarging the visible light absorption range from 410 to 760 nm, thus improving the solar energy utilization. Despite the reduced band gap, the conduction and valance band edges of (Ag, Cu4) codoped g-C3N4 still have sufficient potential to split water. Therefore, to improve the photocatalytic performance under visible light, simultaneous codoping of the Ag single atom and Cu4 cluster on g-C3N4 is an effective strategy. The study provides theoretical support for further optimization of single-atom catalysts.

Strategy and Advancement in Hybrid Hydrogel and Their Applications: Recent Progress and Trends

Advancements in polymers have made significant contribution in diverse application‐oriented fields. The multidisciplinary application of polymers generates a range of strategies, which is applicable in a wide range of biomedicines. Polymeric compounds such as hydrogels have been explored globally as a potent biomaterial that can furnish essential attributes due to their three‐dimensional (3D) soft and highly hydrophilic polymeric network. These hydrogels have been used extensively in various applications due to their biocompatible, biodegradable, and biosorption nature. However, they have some limitations, owing to their soft nature, low mechanical properties, and unsatisfactory degradation profile. Therefore, there is a need to develop novel, stronger, and more durable hybrid hydrogels with enhanced biocompatible and multifunctional properties. The current review gives a broad spectrum of hybrid hydrogels with its importance and significance. Further, the review highlights the strategies of generation of hybrid hydrogels reinforced with nanomaterials, biomaterials, and nanobiocomposites along with their advantages and disadvantages. The review also features various applications of these hybrid hydrogels in the field of biomedicines, photocatalysis, agriculture, and food industry over the last 5 years. This review will give a comprehensive overview to researchers working in the field of hybrid hydrogels development.

In-Situ Anchoring of Co Single-Atom Synergistically with Cd Vacancy of Cadmium Sulfide for Boosting Asymmetric Charge Distribution and Photocatalytic Hydrogen Evolution.

In the context of reshaping the energy pattern, designing and synthesizing high-performance noble metal-free photocatalysts with ultra-high atomic utilization for hydrogen evolution reaction (HER) still remains achallenge. In a streamlined synthesis process, in-situ single atom anchoring is performed in parallel with HER by irradiating a precursory defect-state CdS/Co suspension (Co-DCdS-Ss) system under simulated sunlight and the in-situ synthesizing single-atom Co photocatalyst (Co5:DCdS) exhibits further improved catalytic performance (60.10 mmolg-1h-1) compared with Co-DCdS-Ss (18.09 mmolg-1h-1), reaching an apparent quantum yield of 57.6% at 500nm and a solar-chemical energy conversion efficiency (SCC) of 6.26% at AM 1.5G. In-depth characterization tests and density functional theory (DFT) calculations prove that the anchoring of Co single atom deepens the asymmetric charge distribution of the two-coordination S atom adjacent to the cadmium vacancy (VCd). The synergy between electron delocalization VCd and Co single atom on the catalyst surface is constructed, which bifunctional sites responsible for boosting water adsorption-dissociation and hydrogen evolution. This study advances the understanding of the underlying mechanisms of synergy between surface defects and metal single atoms and opens a new horizon for the development of advanced materials in the field of photocatalysis.

Z-Scheme LaFeO3/Cd0.7Zn0.3S heterojunction based on 3DOM LaFeO3 perovskite for enhanced photocatalytic hydrogen activity

The narrow band gap semiconductor LaFeO3 with ABO3 perovskite structure has been deeply studied in the field of photocatalysis due to its good thermal stability, chemical stability, photoelectric properties and suitable band position. The inverse opal structure gives the material a large specific surface area and increases the adsorption area and active site of the catalyst. In this work, it is reported for the first time that perovskite LaFeO3 inverse opal was applied to photocatalytic hydrogen production. The Cd0.7Zn0.3S QDs were deposited on the skeleton wall of LaFeO3 inverse opal to construct LaFeO3/Cd0.7Zn0.3S binary heterojunction catalyst. The LaFeO3 3DOM can effectively increase the contact area with Cd0.7Zn0.3S QDs with an increase in specific surface area, and the multiple scattering effect improves the efficiency of light utilization. The introduction of Zn2+ ions regulate the band gap position of Cd0.7Zn0.3S QDs and increases the thermodynamic reduction ability of photo generated electrons. The Z-type heterojunction effect formed by LaFeO3 inverse opal and Cd0.7Zn0.3S QDs facilitates the separation and transmission of photo generated charges. The LaFeO3/Cd0.7Zn0.3S heterojunction catalysts achieved a hydrogen production performance of 277.48 μmol/g/h due to the large specific surface area of 3DOM, good light capture ability, band gap regulation of element doping, and efficient charge separation synergistic effect of heterojunction. This work provides new insights into the design and manufacture of perovskite-type 3DOM heterojunction photocatalysts.

Optimizing ligand-to-metal charge transfer in metal–organic frameworks to enhance photocatalytic performance

Metal-organic frameworks (MOFs) have been widely investigated as active photocatalytic material for energy conversion and environmental purification. This review meticulously examines the charge transfer mechanisms within MOFs upon photoexcitation, with a particular emphasis on ligand-to-metal charge transfer (LMCT) and metal-to-ligand charge transfer (MLCT). These processes are essential for the generation and maintenance of effective charge separation, wherein LMCT is especially critical for the photocatalytic applications of MOFs. The analysis begins with an exploration of the charge transfer mechanisms within the MOFs’ structure, assessing the impact of various factors on LMCT, including the metal center, ligand structure, overall spatial configuration and reaction environment. Furthermore, the review provides an in-depth exploration of the advantages and applications of LMCT in photocatalysis. It concludes with an outlook on the future development of LMCT in the field of photocatalysis, underscoring its transformative potential with ongoing research and innovation.

Rapid Charge Transfer Endowed by Hollow‐structured Z‐Scheme Heterojunction for Coupling Benzylamine Oxidation With CO2 Reduction

AbstractIn the field of photocatalysis, ultrafast electron transfer at the interface is the key factor affecting photocatalytic activity. Herein, ultrafast carrier transport is achieved through constructing a Z‐scheme heterojunction of CoSe@Zn0.5Cd0.5S (CoSe@ZCS), which is prepared by in situ growth of ZCS on the ZIF‐67‐derived hollow CoSe. The ultrafast charge transfer at the Z‐scheme heterojunction interface is verified by advanced fs‐transient absorption, which provides vital evidence for the specific mechanism of photocatalytic charge transfer. In addition, the presence of key intermediates (*COOH and C═N) is detected by in‐situ FTIR spectroscopy, which further clarified the mechanism of coupling benzylamine oxidation with CO2 photoconversion. DFT calculations also confirm that the Z‐scheme heterojunction effectively reduces the energy barrier of the rate‐limiting step of *COOH formation, facilitating the photocatalytic CO2 reduction process of ZCS. Benefiting from the ultrafast electron transfer at the interface of the Z‐scheme heterojunction, CoSe@ZCS exhibits excellent bifunctional photocatalytic performance. This work lays the foundation for further exploration of the charge transfer mode at the heterojunction interface to facilitate solar‐driven energy conversion.