The photocatalytic synthesis of hydrogen peroxide (H2O2) has arisen as a sustainable alternative to the energy-demanding anthraquinone method, nonetheless, its efficiency remains unsatisfactory due to fast charge recombination of the photocatalyst and sluggish oxygen reduction. Herein, a flower-like MIL-53-NH2/Zn3In2S6 S-scheme heterojunction constructed via a facile hydrothermal strategy is reported. The unique interface engineering effectively integrates the high redox potential of MIL-53-NH2 with the visible-light responsiveness of Zn3In2S6, enabling efficient photocatalytic hydrogen peroxide production. The optimized MIL/ZIS-3 exhibits an outstanding H2O2 generation rate of 1022.68 μmol·g−1·h−1 without sacrificial agents, surpassing MIL-53-NH2 and Zn3In2S6 by factors of 52.7 and 198.2, respectively. The formation of H2O2 is primarily accomplished by a two-step single-electron reduction pathway of oxygen, with ·O2− acting as the crucial intermediary. This work not only demonstrates the superior synergy of MOF/semiconductor S-scheme heterojunctions in photocatalysis but also provides a conceptual guideline for designing robust and eco-friendly photocatalysts for scalable H2O2 production.
{"title":"Flower-like MIL-53-NH2/Zn3In2S6 S-scheme heterojunction for high-performance photocatalytic H2O2 synthesis","authors":"Yuanyuan Li, Ying Peng, Xinyu Zhang, Tongyu Sun, Yu He, Jiale Liu, Puhui Deng, Linping Zhang, Yu Hou","doi":"10.1016/j.jphotochem.2025.116997","DOIUrl":"10.1016/j.jphotochem.2025.116997","url":null,"abstract":"<div><div>The photocatalytic synthesis of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) has arisen as a sustainable alternative to the energy-demanding anthraquinone method, nonetheless, its efficiency remains unsatisfactory due to fast charge recombination of the photocatalyst and sluggish oxygen reduction. Herein, a flower-like MIL-53-NH<sub>2</sub>/Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> S-scheme heterojunction constructed via a facile hydrothermal strategy is reported. The unique interface engineering effectively integrates the high redox potential of MIL-53-NH<sub>2</sub> with the visible-light responsiveness of Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub>, enabling efficient photocatalytic hydrogen peroxide production. The optimized MIL/ZIS-3 exhibits an outstanding H<sub>2</sub>O<sub>2</sub> generation rate of 1022.68 μmol·g<sup>−1</sup>·h<sup>−1</sup> without sacrificial agents, surpassing MIL-53-NH<sub>2</sub> and Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> by factors of 52.7 and 198.2, respectively. The formation of H<sub>2</sub>O<sub>2</sub> is primarily accomplished by a two-step single-electron reduction pathway of oxygen, with ·O<sub>2</sub><sup>−</sup> acting as the crucial intermediary. This work not only demonstrates the superior synergy of MOF/semiconductor S-scheme heterojunctions in photocatalysis but also provides a conceptual guideline for designing robust and eco-friendly photocatalysts for scalable H<sub>2</sub>O<sub>2</sub> production.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116997"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796960","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Herein, we disclose a new strategy for the synthesis of pyrazolo[4,3-c]quinoline derivatives via redox coupling of aliphatic and aromatic alcohols deriving from natural products under visible light irradiation. Reusable CdS nanoparticles (CdS-NPs) were employed as a photocatalyst. This method provides one-pot synthesis of aldehyde and amine, which are coupled and cyclized selectively to form the desired product. In this strategy, p-toluene sulfonic acid monohydrate (PTSA) has been experimentally identified as a hole scavenger and a Bronsted acid for cyclising imine generated in situ by aldehyde and amine. The substrate scope of 5-(2-nitrophenyl)-1,3-diphenyl-1H-pyrazole and aromatic/aliphatic alcohols is demonstrated with various commercially available alcohols and synthesised heterocyclic nitro precursor. The duality of benzyl alcohol as a H+ source for nitro reduction and a coupling partner with amine has been identified and applied for the pyrazolo-quinoline synthesis. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction analysis (XRD) were utilised to characterise the synthesised CdS-NPs photocatalyst. The UV–vis Diffuse Reflectance Spectroscopy (DRS) and photoluminescence study of the CdS-NPs were utilised to understand the optical properties of the photocatalyst. To examine the surface area and pore volume of the CdS-NPs, we performed Brunauer–Emmett–Teller (BET) analysis. The structural characteristics of CdS-NPs, was examined by XRD before and after the reaction, confirm the stability and good photocatalytic activity of CdS-NPs. To expand the generality of the protocol, we synthesised the bioactive compound showing anti-proliferative properties with our optimised reaction conditions. Overall, this report demonstrates energy and environmental relevance, the comparison with existing catalytic methods, detailed characterisation of CdS-NPs, biomedical relevance, selective oxidation, catalytic recyclability and its stability, role of PTSA, synthetic transformation, substitution tolerance, detailed mechanistic explanation utilising control experiments. This is the first method to couple nitro with alcohol to construct valuable heterocyclic systems under a visible light-mediated recyclable heterogeneous photocatalytic system.
{"title":"Visible-light-driven redox coupling strategy for the synthesis of pyrazolo[4,3-c]quinoline via reusable CdS nanoparticles as photocatalyst","authors":"Markabandhu Shanthi , Vijayakumar Hemamalini , Karuppaiah Perumal , Bhaskaran Shankar , Subburethinam Ramesh","doi":"10.1016/j.jphotochem.2025.116979","DOIUrl":"10.1016/j.jphotochem.2025.116979","url":null,"abstract":"<div><div>Herein, we disclose a new strategy for the synthesis of pyrazolo[4,3-<em>c</em>]quinoline derivatives via redox coupling of aliphatic and aromatic alcohols deriving from natural products under visible light irradiation. Reusable CdS nanoparticles (CdS-NPs) were employed as a photocatalyst. This method provides one-pot synthesis of aldehyde and amine, which are coupled and cyclized selectively to form the desired product. In this strategy, p-toluene sulfonic acid monohydrate (PTSA) has been experimentally identified as a hole scavenger and a Bronsted acid for cyclising imine generated in situ by aldehyde and amine. The substrate scope of 5-(2-nitrophenyl)-1,3-diphenyl-1H-pyrazole and aromatic/aliphatic alcohols is demonstrated with various commercially available alcohols and synthesised heterocyclic nitro precursor. The duality of benzyl alcohol as a H<sup>+</sup> source for nitro reduction and a coupling partner with amine has been identified and applied for the pyrazolo-quinoline synthesis. The scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction analysis (XRD) were utilised to characterise the synthesised CdS-NPs photocatalyst. The UV–vis Diffuse Reflectance Spectroscopy (DRS) and photoluminescence study of the CdS-NPs were utilised to understand the optical properties of the photocatalyst. To examine the surface area and pore volume of the CdS-NPs, we performed Brunauer–Emmett–Teller (BET) analysis. The structural characteristics of CdS-NPs, was examined by XRD before and after the reaction, confirm the stability and good photocatalytic activity of CdS-NPs. To expand the generality of the protocol, we synthesised the bioactive compound showing anti-proliferative properties with our optimised reaction conditions. Overall, this report demonstrates energy and environmental relevance, the comparison with existing catalytic methods, detailed characterisation of CdS-NPs, biomedical relevance, selective oxidation, catalytic recyclability and its stability, role of PTSA, synthetic transformation, substitution tolerance, detailed mechanistic explanation utilising control experiments. This is the first method to couple nitro with alcohol to construct valuable heterocyclic systems under a visible light-mediated recyclable heterogeneous photocatalytic system.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116979"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797052","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Hexavalent chromium (Cr(VI)) wastewater creates a serious concern in terms of health and the environment due to its increased toxicity, mobility, and bioavailability. Photocatalytic reduction of Cr(VI) to its less toxic trivalent form (Cr(III)) is an efficient and sustainable treatment process but is thwarted in practice by low adsorption ability and rapid recombination of charge carriers. In this work, green hydrothermal synthesis of Hydroxyapatite/La3+-doped ZnFe2O4 (HAp/ZFLa) nanocomposites using mussel shell waste as a CaO precursor for hydroxyapatite and Uncaria gambir Roxb. leaf extract as a biogenic capping agent is reported. FESEM, HRTEM, and BET–BJH characterization confirmed that the best HAp/ZFLa-20% nanocomposite had a homogeneous morphology with the particle size of 21.07 nm and high specific surface area of 75.72 m2/g. In addition, La3+ incorporation and HAp composite formation caused band gap narrowing, enhanced visible light absorption, and better charge transfer. Therefore, the HAp/ZFLa-20% nanocomposite exhibited enhanced photocatalytic activity, achieving a maximum Cr(VI) removal efficiency of 99.07 % within 60 min under visible-light irradiation at an initial Cr(VI) concentration of 20 mg/L, using 30 mg/L of catalyst at pH 2, along with a markedly improved adsorption capacity. These results indicate the future potential of green-synthesized HAp/ZFLa nanocomposites as efficient and environmentally friendly photocatalysts for wastewater treatment.
{"title":"Enhanced photocatalytic Cr(VI) reduction using hydroxyapatite/La3+-doped ZnFe2O4 nanocomposites with optimized structural and surface properties","authors":"Ashta Varan Akhmad, Nurul Pratiwi, Rahmayeni, Diana Vanda Wellia, Zulhadjri","doi":"10.1016/j.jphotochem.2025.117000","DOIUrl":"10.1016/j.jphotochem.2025.117000","url":null,"abstract":"<div><div>Hexavalent chromium (Cr(VI)) wastewater creates a serious concern in terms of health and the environment due to its increased toxicity, mobility, and bioavailability. Photocatalytic reduction of Cr(VI) to its less toxic trivalent form (Cr(III)) is an efficient and sustainable treatment process but is thwarted in practice by low adsorption ability and rapid recombination of charge carriers. In this work, green hydrothermal synthesis of Hydroxyapatite/La<sup>3+</sup>-doped ZnFe<sub>2</sub>O<sub>4</sub> (HAp/ZFLa) nanocomposites using mussel shell waste as a CaO precursor for hydroxyapatite and <em>Uncaria gambir</em> Roxb. leaf extract as a biogenic capping agent is reported. FESEM, HRTEM, and BET–BJH characterization confirmed that the best HAp/ZFLa-20% nanocomposite had a homogeneous morphology with the particle size of 21.07 nm and high specific surface area of 75.72 m<sup>2</sup>/g. In addition, La<sup>3+</sup> incorporation and HAp composite formation caused band gap narrowing, enhanced visible light absorption, and better charge transfer. Therefore, the HAp/ZFLa-20% nanocomposite exhibited enhanced photocatalytic activity, achieving a maximum Cr(VI) removal efficiency of 99.07 % within 60 min under visible-light irradiation at an initial Cr(VI) concentration of 20 mg/L, using 30 mg/L of catalyst at pH 2, along with a markedly improved adsorption capacity. These results indicate the future potential of green-synthesized HAp/ZFLa nanocomposites as efficient and environmentally friendly photocatalysts for wastewater treatment.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 117000"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145836789","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-15DOI: 10.1016/j.jphotochem.2025.116984
Xinlin Yang , Yuhang Sun , Yang Wang, Siqi Wang, Tianyu Cui, Hui Li
The photophysical properties of a liquid–solid phase active Schiff-base compound (JDF) were comprehensively investigated using density functional theory (DFT), time-dependent DFT (TDDFT), and quantum mechanics/molecular mechanics (QM/MM) methods. In the liquid phase, JDF undergoes excited-state intramolecular proton transfer (ESIPT) and exhibits pronounced twisted intramolecular charge transfer (TICT) characteristics in acetonitrile (ACN) and tetrahydrofuran (THF). The competition between ESIPT and TICT is proposed to account for the observed photophysics in solution. Triple fluorescence emission arises from the monomer, the ESIPT isomer, and the proton open-loop structure. In contrast, the JDF monomer does not undergo ESIPT in toluene (TOL). Aggregation-induced emission (AIE) of JDF is significantly enhanced with increasing water fraction, attributed to the suppression of intramolecular charge transfer and the expansion of radiative decay channels. In the solid phase, J-aggregation enables barrierless ESIPT by restricting intramolecular NN bond distortion. This work provides molecular-level insight into phase-dependent ESIPT–TICT–AIE processes and offers guidance for designing multi-band, multi-color near-infrared fluorescent probes.
{"title":"Liquid–solid phase regulation of ESIPT–TICT–AIE mechanisms and fluorescent emission in Schiff-base compounds","authors":"Xinlin Yang , Yuhang Sun , Yang Wang, Siqi Wang, Tianyu Cui, Hui Li","doi":"10.1016/j.jphotochem.2025.116984","DOIUrl":"10.1016/j.jphotochem.2025.116984","url":null,"abstract":"<div><div>The photophysical properties of a liquid–solid phase active Schiff-base compound (JDF) were comprehensively investigated using density functional theory (DFT), time-dependent DFT (TDDFT), and quantum mechanics/molecular mechanics (QM/MM) methods. In the liquid phase, JDF undergoes excited-state intramolecular proton transfer (ESIPT) and exhibits pronounced twisted intramolecular charge transfer (TICT) characteristics in acetonitrile (ACN) and tetrahydrofuran (THF). The competition between ESIPT and TICT is proposed to account for the observed photophysics in solution. Triple fluorescence emission arises from the monomer, the ESIPT isomer, and the proton open-loop structure. In contrast, the JDF monomer does not undergo ESIPT in toluene (TOL). Aggregation-induced emission (AIE) of JDF is significantly enhanced with increasing water fraction, attributed to the suppression of intramolecular charge transfer and the expansion of radiative decay channels. In the solid phase, J-aggregation enables barrierless ESIPT by restricting intramolecular N<img>N bond distortion. This work provides molecular-level insight into phase-dependent ESIPT–TICT–AIE processes and offers guidance for designing multi-band, multi-color near-infrared fluorescent probes.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116984"},"PeriodicalIF":4.7,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797048","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-14DOI: 10.1016/j.jphotochem.2025.116992
Lihui Wang , Jinting Ye , Qiang Zhang
In this study, five novel D–A₁–π–A₂-type small-molecule donors (SMDs) based on a triphenylamine (TPA)-benzothiadiazole (BT) framework were designed, namely SM1, SM2, SM3, SM4 and SM5. In these SMDs, F/Cl-modified thienothiophene (TT) units were strategically introduced as π-spacers, and F/Cl-modified dicyanoindenone (IC) units were incorporated as end groups, following the structural pattern of the reference molecule BT-2. Geometric structures of the SMDs were optimized using density functional theory (DFT) at the B3LYP/6-311G(d,p) level, while absorption properties were simulated using time-dependent DFT (TD-DFT) at the CAM-B3LYP/6-311G(d,p) level. A range of other key properties were also systematically investigated, including electronic structures, electron excitation behavior, charge transfer mobility, blend characteristics with the PC₆₁BM acceptor, and overall photovoltaic (PV) performance. The calculated results indicate that all designed SMDs exhibit higher planarity, improved optoelectronic characteristics, and enhanced PV performance compared to BT-2, which can be attributed to the strategic structural modifications proposed in this work. Notably, SM5 showed the broadest absorption band, the lowest HOMO energy level, the highest charge mobility, the strongest interaction energy in the SM5/PC61BM blend and the highest predicted power conversion efficiency (PCE) of 10.30 %. These improvements are ascribed to the synergistic effects of extended π-conjugation through π-spacer engineering, strengthened electron-withdrawing capability from end-group modifications, and optimized geometric and electronic properties resulting from Cl substitution. This work provides a rational design strategy for developing high-efficiency TPA–BT-based SMDs for experimental realization.
{"title":"Exploring the synergy effects of π-spacer engineering, end acceptor group modification and chlorination on TPA-BT based small molecular donors for organic solar cells: A DFT investigation","authors":"Lihui Wang , Jinting Ye , Qiang Zhang","doi":"10.1016/j.jphotochem.2025.116992","DOIUrl":"10.1016/j.jphotochem.2025.116992","url":null,"abstract":"<div><div>In this study, five novel D–A₁–π–A₂-type small-molecule donors (SMDs) based on a triphenylamine (TPA)-benzothiadiazole (BT) framework were designed, namely <strong>SM1</strong>, <strong>SM2</strong>, <strong>SM3</strong>, <strong>SM4</strong> and <strong>SM5</strong>. In these SMDs, F/Cl-modified thienothiophene (TT) units were strategically introduced as π-spacers, and F/Cl-modified dicyanoindenone (IC) units were incorporated as end groups, following the structural pattern of the reference molecule <strong>BT-2</strong>. Geometric structures of the SMDs were optimized using density functional theory (DFT) at the B3LYP/6-311G(d,p) level, while absorption properties were simulated using time-dependent DFT (TD-DFT) at the CAM-B3LYP/6-311G(d,p) level. A range of other key properties were also systematically investigated, including electronic structures, electron excitation behavior, charge transfer mobility, blend characteristics with the PC₆₁BM acceptor, and overall photovoltaic (PV) performance. The calculated results indicate that all designed SMDs exhibit higher planarity, improved optoelectronic characteristics, and enhanced PV performance compared to <strong>BT-2</strong>, which can be attributed to the strategic structural modifications proposed in this work. Notably, <strong>SM5</strong> showed the broadest absorption band, the lowest HOMO energy level, the highest charge mobility, the strongest interaction energy in the <strong>SM5</strong>/PC<sub>61</sub>BM blend and the highest predicted power conversion efficiency (PCE) of 10.30 %. These improvements are ascribed to the synergistic effects of extended π-conjugation through π-spacer engineering, strengthened electron-withdrawing capability from end-group modifications, and optimized geometric and electronic properties resulting from Cl substitution. This work provides a rational design strategy for developing high-efficiency TPA–BT-based SMDs for experimental realization.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116992"},"PeriodicalIF":4.7,"publicationDate":"2025-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797057","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-13DOI: 10.1016/j.jphotochem.2025.116983
Jinyuan Wang , Lili Wang , Qinghua Ma , Haishuang Li , Jie He , Rong Nie , Lingjun Kong , Xiaomei Wang
The development of highly efficient and stable catalysts is a central challenge in achieving photocatalytic water oxidation, a pivotal step in the conversion of solar energy into chemical fuels. In this study, novel BiVO4/CuFe2O4 heterojunctions were synthesized via a solvothermal route followed by calcination under air or argon atmosphere. The resulting BiVO4/CuFe2O4–10 heterojunction exhibited markedly enhanced photocatalytic performance compared to its individual components. Notably, the argon-annealed sample (Ar-BiVO4/CuFe2O4–10) showed a substantial activity improvement, with an oxygen evolution rate of (350.50 μmol·g−1·h−1) 2.69 times higher than that of the air-calcined counterpart (Air-BiVO4/CuFe2O4–10, 130.50 μmol·g−1·h−1), highlighting the crucial influence of the calcination environment. Structural and spectroscopic analyses confirm the successful construction of a Z-scheme heterojunction between n-type BiVO4 and p-type CuFe2O4. This heterostructure significantly improves visible-light absorption and promotes the separation of photogenerated charge carriers relative to pristine BiVO4. Moreover, the Ar-BiVO4/CuFe2O4–10 sample features finer and more uniformly dispersed CuFe2O4 nanoparticles, along with a higher concentration of surface oxygen vacancies compared to the air-treated analog. In situ infrared spectroscopy identified the concurrent formation of *O-O and *OOH intermediates, suggesting that the reaction may proceed via both the lattice oxygen mechanism (LOM) and adsorbate evolution mechanism (AEM). The outstanding performance of Ar-BiVO4/CuFe2O4–10 is attributed to its enhanced water adsorption capacity and the abundance of defective active sites, which collectively facilitate H2O adsorption and activation, leading to a remarkable enhancement in photocatalytic water oxidation activity. This study offers valuable insights for the rational design of high-performance photocatalysts for solar-driven water splitting.
{"title":"BiVO4/CuFe2O4 heterojunction for boosting visible light-driven photocatalytic water oxidation","authors":"Jinyuan Wang , Lili Wang , Qinghua Ma , Haishuang Li , Jie He , Rong Nie , Lingjun Kong , Xiaomei Wang","doi":"10.1016/j.jphotochem.2025.116983","DOIUrl":"10.1016/j.jphotochem.2025.116983","url":null,"abstract":"<div><div>The development of highly efficient and stable catalysts is a central challenge in achieving photocatalytic water oxidation, a pivotal step in the conversion of solar energy into chemical fuels. In this study, novel BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub> heterojunctions were synthesized via a solvothermal route followed by calcination under air or argon atmosphere. The resulting BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub>–10 heterojunction exhibited markedly enhanced photocatalytic performance compared to its individual components. Notably, the argon-annealed sample (Ar-BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub>–10) showed a substantial activity improvement, with an oxygen evolution rate of (350.50 μmol·g<sup>−1</sup>·h<sup>−1</sup>) 2.69 times higher than that of the air-calcined counterpart (Air-BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub>–10, 130.50 μmol·g<sup>−1</sup>·h<sup>−1</sup>), highlighting the crucial influence of the calcination environment. Structural and spectroscopic analyses confirm the successful construction of a <em>Z</em>-scheme heterojunction between n-type BiVO<sub>4</sub> and p-type CuFe<sub>2</sub>O<sub>4</sub>. This heterostructure significantly improves visible-light absorption and promotes the separation of photogenerated charge carriers relative to pristine BiVO<sub>4</sub>. Moreover, the Ar-BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub>–10 sample features finer and more uniformly dispersed CuFe<sub>2</sub>O<sub>4</sub> nanoparticles, along with a higher concentration of surface oxygen vacancies compared to the air-treated analog. In situ infrared spectroscopy identified the concurrent formation of *O-O and *OOH intermediates, suggesting that the reaction may proceed via both the lattice oxygen mechanism (LOM) and adsorbate evolution mechanism (AEM). The outstanding performance of Ar-BiVO<sub>4</sub>/CuFe<sub>2</sub>O<sub>4</sub>–10 is attributed to its enhanced water adsorption capacity and the abundance of defective active sites, which collectively facilitate H<sub>2</sub>O adsorption and activation, leading to a remarkable enhancement in photocatalytic water oxidation activity. This study offers valuable insights for the rational design of high-performance photocatalysts for solar-driven water splitting.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116983"},"PeriodicalIF":4.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Phosphor-based luminescence thermometry has become a very promising technology, which is used for non-contact, remote and spatially resolved temperature sensing in various fields from microelectronics and biomedicine to harsh environment. This method takes advantage of the inherent temperature dependence of specific photoluminescence characteristics of doped inorganic phosphors. In this study, K3LuSi2O7 as the host, doped with rare earth element Europium ion (Eu3+), adjusted the excess degree of K+, and explored antithermal quenching performance. Through thermal activation, we achieved Charge Transfer Band (CTB) edge red-shift, which led to thermally enhanced luminescence under excitation at the position of CTB edge. At 573 K, the comprehensive luminous intensity of the phosphor reached 8.144 times as high as that at 298 K. And the excess degree of K+ also has a positive effect on the antithermal quenching performance of the phosphor. This provides an effective way for thermal enhanced luminescence of Eu3+-doped phosphors. We found that both excitation at the CTB main peak position and excitation at the Eu3+ 4f → 4f transition position exhibited thermal quenching. Therefore, based on completely opposite thermal responses dependent on distinct excitation position, we simultaneously establish two kinds of optical thermometry: single-band radiometric (SBR) optical thermometry and dual-band radiometric optical thermometry, with a maximum sensitivity of 2.701 % @523 K. Moreover, this phosphor exhibits exceptionally stable red emission under specific excitation position. This work provides a novel and viable strategy for optical thermometry using Eu3+-doped phosphors.
{"title":"Dual-mode thermometry design of Eu3+-doped phosphors regulate Antithermal quenching performance through charge transfer band edge red-shift","authors":"Wenting Li, Jiatong Song, Wenxiu Qiu, Chang Liu, Yuchang Yuan, Yuxiang Cui, Ning Guo","doi":"10.1016/j.jphotochem.2025.116990","DOIUrl":"10.1016/j.jphotochem.2025.116990","url":null,"abstract":"<div><div>Phosphor-based luminescence thermometry has become a very promising technology, which is used for non-contact, remote and spatially resolved temperature sensing in various fields from microelectronics and biomedicine to harsh environment. This method takes advantage of the inherent temperature dependence of specific photoluminescence characteristics of doped inorganic phosphors. In this study, K<sub>3</sub>LuSi<sub>2</sub>O<sub>7</sub> as the host, doped with rare earth element Europium ion (Eu<sup>3+</sup>), adjusted the excess degree of K<sup>+</sup>, and explored antithermal quenching performance. Through thermal activation, we achieved Charge Transfer Band (CTB) edge red-shift, which led to thermally enhanced luminescence under excitation at the position of CTB edge. At 573 K, the comprehensive luminous intensity of the phosphor reached 8.144 times as high as that at 298 K. And the excess degree of K<sup>+</sup> also has a positive effect on the antithermal quenching performance of the phosphor. This provides an effective way for thermal enhanced luminescence of Eu<sup>3+</sup>-doped phosphors. We found that both excitation at the CTB main peak position and excitation at the Eu<sup>3+</sup> 4f → 4f transition position exhibited thermal quenching. Therefore, based on completely opposite thermal responses dependent on distinct excitation position, we simultaneously establish two kinds of optical thermometry: single-band radiometric (SBR) optical thermometry and dual-band radiometric optical thermometry, with a maximum sensitivity of 2.701 % @523 K. Moreover, this phosphor exhibits exceptionally stable red emission under specific excitation position. This work provides a novel and viable strategy for optical thermometry using Eu<sup>3+</sup>-doped phosphors.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116990"},"PeriodicalIF":4.7,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797055","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-12DOI: 10.1016/j.jphotochem.2025.116996
Bolong Jiang , Baiqiang Liu , Nan Jiang , Jiacheng Chang , Shuai Wang , Yuanyuan Wang , Yanguang Chen , Huijie Gao
Developing highly efficient non-precious metal catalysts for the oxygen reduction reaction (ORR) in microbial fuel cells (MFCs) remains a critical challenge. Herein, we report a novel strategy to synthesize a highly active ORR catalyst (Co3O4-ZIF/Zn-MnO2) by embedding α-MnO2 and Co3O4 into a mesoporous N-doped carbon matrix. The synthesis initiates with the rational design of a bimetallic leaf-like Co-ZIF/Zn template, which integrates the advantageous properties of ZIF-8 and ZIF-67 to serve as a combined structural and electronic mediator. This template is transformed in situ into Co3O4-ZIF/Zn, followed by the uniform incorporation of α-MnO2 via a straightforward Co2+-mediated reaction that requires no expensive equipment. Our results reveal that the combined strategy of a Co-ZIF/Zn template and MnO2 incorporation facilitates the creation of a defective mesoporous NC architecture, where Zn etching generates abundant oxygen vacancies (Ov). Concurrently, the electronic interaction between α-MnO2 and Co3O4 optimizes the valence states of the metal centers, resulting in a synergistic enhancement. Consequently, the Co3O4-ZIF/Zn-MnO2 composite delivers exceptional ORR performance, surpassing control samples and Pt/C with a superior turnover frequency (TOF), enhanced power density and robust organic pollutant degradation efficiency. This study highlights the pivotal role of structural design and electronic engineering in developing high-performance ORR catalysts for sustainable energy applications.
开发用于微生物燃料电池（mfc）氧还原反应（ORR）的高效非贵金属催化剂仍然是一个严峻的挑战。在此，我们报道了一种新的策略，通过将α-MnO2和Co3O4嵌入到介孔n掺杂碳基体中来合成高活性的ORR催化剂（Co3O4- zif /Zn-MnO2）。首先合理设计了双金属叶状Co-ZIF/Zn模板，该模板结合了ZIF-8和ZIF-67的优点，作为结构和电子的复合介质。该模板在原位转化为Co3O4-ZIF/Zn，然后通过直接的Co2+介导反应均匀地掺入α-MnO2，不需要昂贵的设备。我们的研究结果表明，Co-ZIF/Zn模板和MnO2掺入的组合策略有助于创建有缺陷的介孔NC结构，其中Zn蚀刻产生丰富的氧空位（Ov）。同时，α-MnO2与Co3O4之间的电子相互作用优化了金属中心的价态，导致了协同增强。因此，Co3O4-ZIF/Zn-MnO2复合材料具有卓越的ORR性能，超越对照样品和Pt/C，具有优越的周转频率（TOF），增强的功率密度和强大的有机污染物降解效率。本研究强调了结构设计和电子工程在开发可持续能源应用的高性能ORR催化剂中的关键作用。
{"title":"Fabrication of MnO2 modified N-doped carbon-based Co3O4 for dual roles in MFC energy conversion and pollutant degradation","authors":"Bolong Jiang , Baiqiang Liu , Nan Jiang , Jiacheng Chang , Shuai Wang , Yuanyuan Wang , Yanguang Chen , Huijie Gao","doi":"10.1016/j.jphotochem.2025.116996","DOIUrl":"10.1016/j.jphotochem.2025.116996","url":null,"abstract":"<div><div>Developing highly efficient non-precious metal catalysts for the oxygen reduction reaction (ORR) in microbial fuel cells (MFCs) remains a critical challenge. Herein, we report a novel strategy to synthesize a highly active ORR catalyst (Co<sub>3</sub>O<sub>4</sub>-ZIF/Zn-MnO<sub>2</sub>) by embedding α-MnO<sub>2</sub> and Co<sub>3</sub>O<sub>4</sub> into a mesoporous N-doped carbon matrix. The synthesis initiates with the rational design of a bimetallic leaf-like Co-ZIF/Zn template, which integrates the advantageous properties of ZIF-8 and ZIF-67 to serve as a combined structural and electronic mediator. This template is transformed in situ into Co<sub>3</sub>O<sub>4</sub>-ZIF/Zn, followed by the uniform incorporation of α-MnO<sub>2</sub> via a straightforward Co<sup>2+</sup>-mediated reaction that requires no expensive equipment. Our results reveal that the combined strategy of a Co-ZIF/Zn template and MnO<sub>2</sub> incorporation facilitates the creation of a defective mesoporous NC architecture, where Zn etching generates abundant oxygen vacancies (O<sub>v</sub>). Concurrently, the electronic interaction between α-MnO<sub>2</sub> and Co<sub>3</sub>O<sub>4</sub> optimizes the valence states of the metal centers, resulting in a synergistic enhancement. Consequently, the Co<sub>3</sub>O<sub>4</sub>-ZIF/Zn-MnO<sub>2</sub> composite delivers exceptional ORR performance, surpassing control samples and Pt/C with a superior turnover frequency (TOF), enhanced power density and robust organic pollutant degradation efficiency. This study highlights the pivotal role of structural design and electronic engineering in developing high-performance ORR catalysts for sustainable energy applications.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116996"},"PeriodicalIF":4.7,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145796962","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
We present a pulsed electrodeposition strategy for synthesizing mixed-phase 1 T/2H-MoS2 quantum dots (QDs), yielding nanostructured films with remarkable catalytic performance. At an ultralow catalyst loading of 8 mg·L−1, the MoS2 QDs achieved 98 % degradation of methylene blue dye under solar simulator illumination, with a high reaction rate of 2 × 10−2 min−1. The QDs demonstrated strong visible-light activity and maintained 78 % efficiency after four consecutive cycles, confirming their long-term operational stability. The enhanced catalytic activity is attributed to the synergistic interplay of 1 T-MoS2 and 2H-MoS2 phases and the quantum confinement, which facilitates efficient charge separation and extends light absorption. Mechanistic insights highlight the key roles of reactive oxygen species and charge-transfer processes in the degradation pathway. These findings position electrodeposited mixed-phase 1 T/2H-MoS2 QDs as promising, scalable photocatalysts for solar-driven wastewater remediation.
{"title":"Mixed-phase electrodeposited MoS2 quantum dots for solar-driven dye removal","authors":"Abderrahim Bayou , Bouchra Asbani , Ahmed Kotbi , Mickael Lejeune , Nitul Rajput , Youssef Doubi , Mustapha Jouiad","doi":"10.1016/j.jphotochem.2025.116987","DOIUrl":"10.1016/j.jphotochem.2025.116987","url":null,"abstract":"<div><div>We present a pulsed electrodeposition strategy for synthesizing mixed-phase 1 T/2H-MoS<sub>2</sub> quantum dots (QDs), yielding nanostructured films with remarkable catalytic performance. At an ultralow catalyst loading of 8 mg·L<sup>−1</sup>, the MoS<sub>2</sub> QDs achieved 98 % degradation of methylene blue dye under solar simulator illumination, with a high reaction rate of 2 × 10<sup>−2</sup> min<sup>−1</sup>. The QDs demonstrated strong visible-light activity and maintained 78 % efficiency after four consecutive cycles, confirming their long-term operational stability. The enhanced catalytic activity is attributed to the synergistic interplay of 1 T-MoS<sub>2</sub> and 2H-MoS<sub>2</sub> phases and the quantum confinement, which facilitates efficient charge separation and extends light absorption. Mechanistic insights highlight the key roles of reactive oxygen species and charge-transfer processes in the degradation pathway. These findings position electrodeposited mixed-phase 1 T/2H-MoS<sub>2</sub> QDs as promising, scalable photocatalysts for solar-driven wastewater remediation.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116987"},"PeriodicalIF":4.7,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145747537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-11DOI: 10.1016/j.jphotochem.2025.116993
Dongxiao E. , Jingping Ouyang , Xikang Wang , Jiayu He , Weimei Gao , Lukang Cao , Song You , Xian Jia
The photocatalytic direct hydrogen atom transfer (d-HAT) strategy enables highly atom-economical synthesis by utilizing inactivated CH bonds, excelling indirect HAT in elimination of additional HAT reagents and simple catalytic cycle. To address the limitations of traditional d-HAT photocatalysts that require heating and anaerobic conditions, theory-guided reaction design and verification were implemented with anthraquinone catalysts. The high bond dissociation energy (BDE) allows the reaction to proceed at room temperature with flexible substrate selectivity yet invariant regioselectivity, extending the reaction repertoire to Giese addition and addition-elimination reactions including 47 substrates with 62 % – 94 % yields. The distinct mechanism demonstrates broad substrate compatibility, including diverse CH donors such as ethers, alcohols, and inactivated cycloalkanes, which further extended to drug intermediates (vonoprazan). In terms of practicality, the Giese addition reaction can be conducted under flow conditions, driven by natural sunlight, and integrated with Knoevenagel condensation for one-pot cascade reactions, where the catalysts' sustainability was further enhanced by immobilization to maintain 84 % activity after 6 cycles. Based on comprehensive mechanism experiments, a plausible and well-supported d-HAT reaction mechanism was proposed, delivering an expandable repertoire of CH functionalization in d-HAT manner.
{"title":"Direct hydrogen atom transfer mediated C–H functionalization enabled by an anthraquinone-based photocatalyst","authors":"Dongxiao E. , Jingping Ouyang , Xikang Wang , Jiayu He , Weimei Gao , Lukang Cao , Song You , Xian Jia","doi":"10.1016/j.jphotochem.2025.116993","DOIUrl":"10.1016/j.jphotochem.2025.116993","url":null,"abstract":"<div><div>The photocatalytic direct hydrogen atom transfer (<em>d</em>-HAT) strategy enables highly atom-economical synthesis by utilizing inactivated C<img>H bonds, excelling indirect HAT in elimination of additional HAT reagents and simple catalytic cycle. To address the limitations of traditional <em>d</em>-HAT photocatalysts that require heating and anaerobic conditions, theory-guided reaction design and verification were implemented with anthraquinone catalysts. The high bond dissociation energy (BDE) allows the reaction to proceed at room temperature with flexible substrate selectivity yet invariant regioselectivity, extending the reaction repertoire to Giese addition and addition-elimination reactions including 47 substrates with 62 % – 94 % yields. The distinct mechanism demonstrates broad substrate compatibility, including diverse C<img>H donors such as ethers, alcohols, and inactivated cycloalkanes, which further extended to drug intermediates (vonoprazan). In terms of practicality, the Giese addition reaction can be conducted under flow conditions, driven by natural sunlight, and integrated with Knoevenagel condensation for one-pot cascade reactions, where the catalysts' sustainability was further enhanced by immobilization to maintain 84 % activity after 6 cycles. Based on comprehensive mechanism experiments, a plausible and well-supported <em>d</em>-HAT reaction mechanism was proposed, delivering an expandable repertoire of C<img>H functionalization in <em>d</em>-HAT manner.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"474 ","pages":"Article 116993"},"PeriodicalIF":4.7,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145797053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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