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Chinese Journal of Catalysis
2024, Vol. 57
Online: 18 February 2024

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Cover: Professors Lin Zhuang, Li Xiao and co-workers used mesoporous carbon as anode catalyst supports in alkaline polymer electrolytes membrane fuel cells, which significantly alleviated the anode flooding issue at low inlet gas flow. This finding provides new way to optimize water management under realistic operating conditions. Read more about the article behind the cover on page 51–58.

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Defect and interface engineering for promoting electrocatalytic N-integrated CO2 co-reduction Zhichao Wang, Mengfan Wang, Yunfei Huan, Tao Qian, Jie Xiong, Chengtao Yang, Chenglin Yan 2024, 57:  1-17.  DOI: 10.1016/S1872-2067(23)64588-7 Abstract ( 299 )   HTML ( 36 )   PDF (6494KB) ( 188 )   Current industrial manufacturing producing chemicals and fertilizers usually requires harsh conditions with high energy consumption, and is thus a major contributor to global carbon dioxide (CO2) emissions. With the increasing demand for sustainability, the scientific researchers are endeavoring to develop efficient carbon-neutral and nitrogen-cycle strategies that utilize sustainable energy storage and conversion technologies. In this context, electrocatalytic coupling of CO2 and nitrogenous species (such as nitrogen, ammonia, nitrate, and nitrite) to high-value-added chemicals and fuels with rationally designed electrocatalysts is a promising strategy to restore the imbalanced carbon neutrality and nitrogen cycle. However, despite considerable breakthrough in recent years, the electrocatalytic N-integrated CO2 co-reduction still suffers from the unsatisfactory activity and selectivity, as well as the ambiguous C-N coupling mechanisms. In this review, we summarize the recent progress on defect and interface engineering strategies to design highly efficient electrocatalysts for electrochemical C-N coupling. Especially, the structure-activity relationships between defect/interface engineering and electrochemical performance are systematically illustrated using representative experimental data and theoretical calculations. Moreover, the major challenge and future development direction of defect and interface engineering are also proposed. It is hoped that this work can provide guidance and enlightenment for the development of electrochemical C-N coupling technology.

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Emerging polynary bismuth-based photocatalysts: Structural classification, preparation, modification and applications Min Li, Shixin Yu, Hongwei Huang 2024, 57:  18-50.  DOI: 10.1016/S1872-2067(23)64593-0 Abstract ( 841 )   HTML ( 39 )   PDF (24693KB) ( 262 )   Photocatalysis is widely recognized as a promising technique for addressing energy and environmental challenges. Exploring novel photocatalysts represents a crucial avenue for advancing the development of photocatalytic technology. Bismuth (Bi)-based photocatalysts have garnered significant attention due to their distinctive crystal structure, favorable hybrid electronic band structure and diverse composition. In recent years, numerous polynary Bi-based (PBB) photocatalysts have been investigated, which exhibit excellent photocatalytic performance. However, most reviews still primarily focus on summarizing traditional materials, it is necessary and urgent to provide a comprehensive review of emerging PBB photocatalysts reported in recent years. This review encompasses the latest advancements in emerging PBB photocatalysts over the past decade (approximately 60 species), covering crystal structure, synthesis method, modification approaches and application areas. This review provides a concise summary and offers insight into future research trends of emerging PBB photocatalysts and guidance for finding suitable applications based on their crystal structures.

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Alleviating anode flooding by mesoporous carbon supports for alkaline polymer electrolyte fuel cells Wenyong Jiang, Chuangxin Ge, Gongwei Wang, Juntao Lu, Li Xiao, Lin Zhuang 2024, 57:  51-58.  DOI: 10.1016/S1872-2067(23)64564-4 Abstract ( 237 )   HTML ( 14 )   PDF (3013KB) ( 81 )   Supporting Information Water management is one of the critical issues affecting the performance and stability of alkaline polymer electrolyte fuel cells (APEFCs). This study focuses on the effect of carbon supports on the water management of APEFCs. A series of carbon-supported Ru catalysts (Ru/MCP-x) were prepared using mesoporous carbon powder (MCP-x) with three-dimensional through-nanopore structures as supports and compared with Ru/XC72. The results show that although the catalysts’ hydrogen oxidation reaction (HOR) catalytic activities are similar in KOH solutions, the APEFCs performance can be severely different. APEFCs assembled with Ru/MCP-x and Ru/XC72 (noted as Ru/MCP-x cell and Ru/XC72 cell) have little performance difference at high inlet H2 flow (1000 mL/min), but have a noticeable difference at low inlet H2 flow (200 mL/min). By combining the electrochemical AC impedance and distribution of relaxation time (DRT) method, we quantitatively identify that severe gas transfer resistance occurred in the anode catalyst layer of the Ru/XC72 cell under low inlet H2 flow, which is more in line with the actual APEFCs operating conditions, led to considerable degradation of the Ru/XC72 cell performance. The high gas transfer resistance is later ascribed to the anode flooding by combining the voltammetry curves and DRT plots. In contrast, for Ru/MCP-x cells, increasing the carbon supports' mesopore diameter dramatically reduced the gas transfer resistance and mitigated the anode flooding. This study shows a quantitative comparison of the impacts of different carbon supports on APEFCs performance and gas transfer resistance, indicating that mesoporous carbon materials have the potential to be supports for APEFCs anode catalysts to alleviate the anode flooding.

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Unraveling the electro-oxidation steps of methanol on a single nanoparticle by in situ nanoplasmonic scattering spectroscopy Xiangqi Zhou, Lili Li, Jun-Gang Wang, Zhanbo Li, Xiji Shao, Fupeng Cheng, Linjuan Zhang, Jian-Qiang Wang, Akhil Jain, Tao Lin, Chao Jing 2024, 57:  59-67.  DOI: 10.1016/S1872-2067(23)64589-9 Abstract ( 493 )   HTML ( 34 )   PDF (1722KB) ( 174 )   Supporting Information Understanding the mechanism of methanol oxidation reaction (MOR) remains a challenge in the development of direct methanol fuel cells. Large-scale investigations of the MOR encounter issues related to mass transfer and averaging effects. To address these limitations, exploring the MOR on the surfaces of individual nanocatalyst and precisely identifying the reaction steps can yield valuable insights into the underlying pathways. In this study, we employed in situ nanoplasmonic resonance scattering spectroscopy to dynamically monitor the MOR process on single gold nanorod particles (GNPs) and Pt-coated gold nanoparticles (Pt-GNPs). We observed the evolution of metal hydroxides, which was assumed as the active species. Notably, the dynamic behavior of the surface atomic layers revealed the rate-determining steps for both the GNPs and Pt-GNPs, indicating competitive adsorption of intermediates on the nanocatalyst surface. The resulting inherent reaction mechanism highlights the thermodynamics-dependent catalysts’ redox processes and their surface adsorptions, which holds significance for advancing highly active MOR catalysts.

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Integration of theory prediction and experimental electrooxidation of glycerol on NiCo2O4 nanosheets Yan Duan, Mifeng Xue, Bin Liu, Man Zhang, Yuchen Wang, Baojun Wang, Riguang Zhang, Kai Yan 2024, 57:  68-79.  DOI: 10.1016/S1872-2067(23)64585-1 Abstract ( 338 )   HTML ( 24 )   PDF (5921KB) ( 135 )   Supporting Information Electrocatalytic refinery of low-value biomass-based glycerol into value-added chemicals formic acid (FA) is an attractive alternative to traditional thermochemical refineries. However, constructing non-precious catalysts with abundant active hydroxyl (OH*) is the main obstacle to the electrocatalytic glycerol oxidation reaction (EGOR). Herein, we combine density functional theory (DFT) and experiments to investigate EGOR over the finely constructed NiCo2O4 nanosheets. DFT results firstly indicate that the NiCo2O4 nanosheets exhibit the highly hydroxylated (311)-OH* surface with the lowest Gibbs free energy, which significantly improves the electrochemical reaction kinetics and can achieve desirable FA yield by adjusting the adsorption energy of the adsorption intermediate. Following the theoretical prediction, ultrathin NiCo2O4 nanosheets (~1.70 nm) are fabricated by a facile electrodeposition method with sufficient OH* on the surface. The charge-transfer resistance of NiCo2O4 nanosheets in EGOR is only 0.94 Ω and the anode power consumption can be reduced by up to 320 mV at 10 mA cm-2, keeping the high glycerol conversion (89%) and FA selectivity (70%) during the 120-h stability test. DFT calculations and experimental tools (e.g., multi-potential step experiments, operational electrochemical impedance spectroscopy) confirm that OH* in-situ generated on the thin nanosheets structure is essential in facilitating charge transfer between catalysts and adsorbed molecules to enhance C-C bond cleavage. This work offers a guideline for the rational design of robust catalysts for the selective upgrading of biomass-derived chemicals.

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Synergistic promotion by highly active square-shaped lead oxide and visualized electrolyzer for enhanced electrochemical ozone production Jia Liu, Shibin Wang, Jinfu Cai, Lizhen Wu, Yun Liu, Jiahui He, Zaixiang Xu, Xiaoge Peng, Xing Zhong, Liang An, Jianguo Wang 2024, 57:  80-95.  DOI: 10.1016/S1872-2067(23)64614-5 Abstract ( 181 )   HTML ( 9 )   PDF (26025KB) ( 56 )   Supporting Information Electrochemical ozone production (EOP) is an intrinsically safe technology compared to Corona discharge methods for ozone generation. However, EOP technology exhibits higher electrical utility demand. Herein, a square-shaped lead oxide (PbOx-CTAB-120) electrocatalyst with outstanding EOP activity has been successfully prepared by a simple method. Then the PbOx-CTAB-120 was assembled into a newly visualized EOP electrolyzer (with parallel flow field) at 1.0 A cm-2 in ultrapure water. The gaseous ozone yield reached 588 mg h-1 g-1catalyst, corresponding to a specific energy consumption (PEOP) of 56 Wh g-1gaseous ozone. In-situ 18O isotope-labelled differential electrochemical mass spectrometry reveals that PbOx-CTAB-120 undergoes phase shuttling to β-PbO2 via the lattice oxygen oxidation mechanism pathway. Furthermore, density functional theory calculations for multiple reaction pathways on the Pb3O4 (110) surface also demonstrated the participance of lattice oxygen in the EOP process, with the results show that the oxygen vacancy generated from lattice oxygen migration could effectively stabilize the OOH* and O2* reaction intermediate in contrast to the adsorbate evolution mechanism. Therefore, the presence of highly stabilized surfaces Pb3O4 (110) on PbOx-CTAB-120 before phase shuttling and the stabilization of β-PbO2 (101) and β-PbO2 (110) crystalline surfaces after phase shuttling allowed PbOx-CTAB-120 to maintain its excellent EOP activity and stability. Moreover, based on computational fluid dynamics simulations and experimental observations, the parallel flow field design facilitated efficient mass transfer of the gaseous product (O2+O3) and effective thermal dissipation of the system. In addition, the high activity electrocatalyst coupled with the optimized EOP electrolyzer enabled efficient in-situ degradation of organic species.

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Electrocatalytic reduction of CO2 with enhanced C2 liquid products activity by the synergistic effect of Cu single atoms and oxygen vacancies Quanquan Bie, Haibo Yin, Yunlong Wang, Haiwei Su, Yue Peng, Junhua Li 2024, 57:  96-104.  DOI: 10.1016/S1872-2067(23)64587-5 Abstract ( 456 )   HTML ( 26 )   PDF (5343KB) ( 149 )   Supporting Information Electrochemical conversion of CO2 to high energy density multi-carbon liquid phase fuels such as ethanol offers a promising strategy to realize carbon neutrality. However, the selectivity of value-added C2 liquid products is still deemed unsatisfactory currently due to the high overpotential, poor selectivity, and the difficulty of the C-C coupling process. Herein, we report that Cu single atoms (SAs) on hydrogen reduced UIO66-NH2 (named Cu SAs/UIO-H2) achieve C2 liquid products Faraday efficiency (FE) of 58.62% and ethanol FE of 46.28% at a low potential of -0.66 V versus the reversible hydrogen electrode. The ethanol FE of Cu SAs/UIO-H2 is 9.61 times higher than UIO66-NH2. Moreover, the experimental results and theoretical calculations demonstrate that Cu SAs and oxygen vacancies (OVs) synergistically promote the generation of *HCCOH intermediate, thus accelerating the formation of ethanol. This work offers deeper understanding at the atomic scale for designing high-performance electrocatalysts for CO2 conversion to valuable liquid fuels.

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Catalytic propane dehydrogenation by anatase supported Ni single-atom catalysts Qian Zhang, Xunzhu Jiang, Yang Su, Yang Zhao, Botao Qiao 2024, 57:  105-113.  DOI: 10.1016/S1872-2067(23)64584-X Abstract ( 319 )   HTML ( 19 )   PDF (6303KB) ( 174 )   Supporting Information With the increasing production of propane from shale gas and the growing demand for propylene, propane dehydrogenation (PDH) has gained significant attention as a promising route for the on-purpose production of propylene. As a cheap yet efficient catalyst, Ni-based catalysts have attracted interest because of its ability to activate alkane. Single-atom catalysts (SACs) can maximize the metal atom utilization. Here, we demonstrate that anatase TiO2 supported Ni SAC (Ni1/A-TiO2) exhibits not only superior intrinsic activity and propylene selectivity but also much better stability than the corresponding Ni nanoparticle (NP) catalyst (NiNP/A-TiO2) in PDH reaction at 580 °C. The rate of propylene production on Ni1/A-TiO2 is about 1.96 molC3H6 gNi-1 h-1, about 65 times higher than that of NiNP/A-TiO2 sample (0.03 molC3H6 gNi-1 h-1). In combination of high-angle annular dark-field scanning transmission electron microscopy, in-situ diffuse reflectance infrared Fourier transform spectra, in-situ X-ray photoelectron spectroscopy and X-ray absorption spectroscopy characterizations, we confirm that the Ni SAC mainly contains individual Ni atom singly dispersed on the support in positive Ni (II) valence state. In addition, as a result of strong metal-support interaction (SMSI) between Ni NP and TiO2 carrier under reduced conditions, the Ni NPs sites are encapsulated by TiOx overlayer (~2 nm thick) thus display poor reaction performance.

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Pickering emulsion stabilized with charge separation and transfer modulated photocatalyst for enzyme-photo-coupled catalysis Jiali Liu, Huicong Dai, Xin Liu, Yiqi Ren, Maodi Wang, Qihua Yang 2024, 57:  114-122.  DOI: 10.1016/S1872-2067(23)64586-3 Abstract ( 215 )   HTML ( 19 )   PDF (5984KB) ( 88 )   Supporting Information Biocatalytic reduction is extensively employed in chemical and pharmaceutical industries due to its notable advantages including high activity, selectivity and mild reaction conditions, however, the stoichiometric use of the expensive NADH (reduced form of nicotinamide adenine dinucleotide) hinders its widespread application. Despite the persisting challenges of low charge separation efficiency and limited solubility of organic substrates in aqueous phase, in situ photocatalytic NADH regeneration remains a promising solution. Herein, we report the construction of an enzyme-photo-coupled catalytic system in Pickering emulsion droplet, which was stabilized by a charge separation and transfer modulated photocatalyst. The photocatalyst integrated with visible light driven conjugated polymer, TiO2 and electron mediator greatly enhanced the cascade electron transfer from photocatalyst to NAD+. Consequently, NADH production rate over the integrated photocatalyst reaches as high as 2.4 mmol·g-1·h-1 under visible light irradiation, 12 folds higher than the corresponding physical mixture. Furthermore, the enzyme-photo-coupled catalytic system was constructed with alcohol dehydrogenase/NAD+ confined in the emulsion droplet and photocatalyst assembled at the oil-water interface. The photoactive emulsion continuously catalyzed the n-butyaldehyde reduction to accumulate 16.1 mmol·L-1 butanol, equivalent to 14 cycles for NADH regeneration under visible light irradiation. The primary result demonstrates the potential application prospect of Pickering emulsion in enzyme-photo-coupled catalysis due to the facilitated charge transfer from photocatalyst to NAD+ and fast mass diffusion attributed to the large interfacial area of water and oil.

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Oxygen vacancies mediated ultrathin Bi4O5Br2 nanosheets for efficient piezocatalytic peroxide hydrogen generation in pure water Hao Cai, Fang Chen, Cheng Hu, Weiyi Ge, Tong Li, Xiaolei Zhang, Hongwei Huang 2024, 57:  123-132.  DOI: 10.1016/S1872-2067(23)64591-7 Abstract ( 379 )   HTML ( 20 )   PDF (5298KB) ( 171 )   Supporting Information The industrial anthraquinone method for H2O2 production has the serious flaws, such as high pollution and energy consumption. Piezocatalytic H2O2 evolution has been proven as a promising strategy, but its progress is hindered by unsatisfied energy conversion efficiency. Hence, we report the efficient piezocatalytic H2O2 generation in pure water over oxygen vacancies mediated ultrathin Bi4O5Br2 nanosheets (~5 nm). Oxygen vacancies and thin nanostructure not only enhance the piezoelectric properties of Bi4O5Br2, but also advance the separation and transfer of piezoinduced charges. Moreover, density functional theory (DFT) calculations also prove that the introduction of oxygen vacancies enhances the O2 adsorption and activation ability with largely decreased Gibbs free energy of the reaction pathway. Profiting from these advantages, ultrathin Bi4O5Br2 nanosheets optimized by oxygen vacancies exhibit a prominent H2O2 evolution rate of 620 µmol g-1 h-1 in pure water and 2700 µmol g-1 h-1 in sacrificial system, dominated by a two-step single electron reaction, which exceeds most of reported piezocatalysts. This work demonstrates that oxygen vacancies and ultrathin structure can synergistically enhance the piezocatalytic performance, which presents perspectives into exploring the strategies of defects and nanostructure fabrication for promoting piezocatalytic activity.

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Self-adjusted reaction pathway enables efficient oxidation of aromatic C-H bonds over zeolite-encaged single-site cobalt catalyst Jian Dang, Weijie Li, Bin Qin, Yuchao Chai, Guangjun Wu, Landong Li 2024, 57:  133-142.  DOI: 10.1016/S1872-2067(23)64579-6 Abstract ( 744 )   HTML ( 26 )   PDF (2061KB) ( 252 )   Supporting Information The selective oxidation of aromatic C-H bonds to high value-added oxygenated products with molecular oxygen remains a key challenge in heterogeneous catalysis. Eligible heterogeneous catalysts are pursued and the reaction mechanism is hotly debated. Herein, we report that zeolite-encaged single-site cobalt ions can efficiently catalyze the model reaction of ethylbenzene aerobic oxidation to acetophenone, outperforming the industrial benchmark catalyst cobalt naphthenate under identical conditions. The self-accelerating phenomenon is observed in the progress of ethylbenzene aerobic oxidation, corresponding to the self-adjusted reaction pathway as revealed by kinetic studies and density functional theory calculations. The formation of reactive O* species on Co sites, resembling the well-known α-O on Fe sites, is identified to be responsible for the self-adjusted reaction pathway of aromatic C-H bond oxidation.

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Hollow spherical covalent organic framework supported gold nanoparticles for photocatalytic H2O2 production Yong Zhang, Junyi Qiu, Bicheng Zhu, Guotai Sun, Bei Cheng, Linxi Wang 2024, 57:  143-153.  DOI: 10.1016/S1872-2067(23)64580-2 Abstract ( 560 )   HTML ( 30 )   PDF (2716KB) ( 184 )   Supporting Information Covalent organic frameworks (COFs) are porous crystalline materials with promising applications in photocatalysis, but their performance is greatly hampered by the fast recombination of photogenerated carriers. Herein, a hollow spherical COF was synthesized via the condensation polymerization of 1,3,5-tris(4-aminophenyl)benzene and 1,3,5-benzenetricarbaldehyde, and Au nanoparticles were in-situ deposited onto the COF through NaBH4 reduction to ameliorate the photocatalytic performance. The composite exhibits impressive photocatalytic H2O2-production performance with the highest H2O2-evolution rate of 6067 μmol g−1 h−1 under visible light irradiation, which is about 1.9 times that of the pristine COF. The enhanced photocatalytic activity was ascribed to improved light absorption, abundant active Au sites, and efficient transfer and separation of photogenerated carriers in space. This work provides an avenue for designing high-performance H2O2-production photocatalysts by decorating porous COFs with active noble-metal sites.

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Controlled construction of Co3S4@CoMoS yolk-shell sphere for efficient hydrodesulfurization promoted by hydrogen spillover effect Wenjing Bao, Chao Feng, Shuyan Ma, Dengwei Yan, Cong Zhang, Changle Yue, Chongze Wang, Hailing Guo, Jiqian Wang, Daofeng Sun, Yunqi Liu, Yukun Lu 2024, 57:  154-170.  DOI: 10.1016/S1872-2067(23)64573-5 Abstract ( 229 )   HTML ( 8 )   PDF (5067KB) ( 88 )   Supporting Information A yolk-shell structured Co3S4@CoMoS catalyst was prepared through Oswald ripening method and subsequently used for hydrodesulfurization (HDS) reaction. The shells, constructed from Co-promoted MoS2 nanosheets, possess abundant active sites and facilitate the adsorption of reactants through the development of pore channels. The MoS2 sheets are arranged in a staggered and convoluted manner, creating numerous defect sites. The shorter MoS2 slabs provide a wide distribution of reactive sites, ensuring efficient reactions. The Co3S4 species within the inner core acts as an auxiliary active phase, inducing the hydrogen spillover effect in the HDS system. This facilitates the transfer of active hydrogen species to the CoMoS shell, where both CoMoS and Co3S4 phases synergistically enhance the HDS reaction. The Co3S4@CoMoS catalyst achieved up to 99.2% dibenzothiophene (DBT) conversion and 94.9% 4,6-dimethyldibenzothiophene conversion at the lower dosage (30 mg). The structure-activity relationships between active phase and HDS activity were investigated via in-situ infrared spectroscopy and other characterizations as well as density functional theory calculations.

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Perylene diimide covalent organic frameworks super-reductant for visible light-driven reduction of aryl halides Yucheng Jin, Xiaolin Liu, Chen Qu, Changjun Li, Hailong Wang, Xiaoning Zhan, Xinyi Cao, Xiaofeng Li, Baoqiu Yu, Qi Zhang, Dongdong Qi, Jianzhuang Jiang 2024, 57:  171-183.  DOI: 10.1016/S1872-2067(23)64592-9 Abstract ( 326 )   HTML ( 16 )   PDF (3814KB) ( 140 )   Supporting Information In recent years, there has been a growing interest in the utilization of molecular photocatalysts in their radical ionic forms, especially as visible-light super-reductants. These catalysts exhibit remarkable capabilities in facilitating otherwise inert high-potential organic reactions, such as the reduction of aryl halides to aryl radicals. However, the development of heterogeneous super-reductants has lagged behind due to the deactivation effect caused by molecular aggregation. This study presents a novel approach to address this limitation by heterogenizing perylene diimides (PDIs) super-reductants with a consecutive photo-induced electron transfer mechanism into two-dimensional donor-acceptor (D-A) covalent organic frameworks (COFs). Both COFs, possessing D-A electronic structures and photothermal effects, demonstrated superior visible-light photocatalytic performance compared to their homogeneous counterparts. They achieved up to 99% conversion in the dehalogenation of aryl halides, primarily through a hydrogen atom trapping aryl radical mechanism. Additionally, we conducted a comparative investigation of the excited states of radical anionic D-A-type COFs and DPPDI using femtosecond transient absorption spectroscopy. Notably, the lifetimes of COFs were significantly prolonged, measuring 210 and 260 ps, respectively, compared to the 150 ps lifetime of (DPPDI•−). This study offers valuable insights into the design of efficient free radical ion-type photocatalysts, with potential applications in various chemical transformations.