Journal of Photochemistry and Photobiology A-chemistry最新文献

{"title":"Probing the role of fluorination in dithienopyrrole-benzothiadiazole donor-acceptor copolymers: Experimental and computational perspectives","authors":"Bakhet A. Alqurashy , Osama Alharbi , Shabbir Muhammad , Aijaz Rasool Chaudhry , Ahmed Iraqi","doi":"10.1016/j.jphotochem.2025.116641","DOIUrl":"10.1016/j.jphotochem.2025.116641","url":null,"abstract":"<div><div>Two D–A semiconducting copolymers, <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT</strong> and <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong>, in which dithienopyrrole (the electron donor) were connected with fluorinated and non-fluorinated quinoxaline (the electron acceptors). <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT</strong> and <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong> were fabricated via a Stille coupling reaction for application as p-type materials in polymer solar cells (PSCs). Different analysis and characterizations, including ultraviolet-visible (UV–Vis) spectroscopy, cyclic voltammetry (CV), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and proton nuclear magnetic resonance (<sup>1</sup>H NMR), were performed on both copolymers, <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT</strong> and <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong>, in order to investigate their electrochemical, optical and thermal properties as well as their molecular organization in the solid state. The influence of inclusion of two fluorine atoms on the benzothiadiazole unit is thoroughly investigated. The two copolymers displayed decomposition temperatures of about 400 °C. The nonfluorinated polymer, <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT</strong>, displayed a narrower E<sub>g</sub><sup>opt</sup> of 1.52 eV and a shallower HOMO level of – 4.94 eV relative to the fluorinated polymer (<strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong>) which has a E<sub>g</sub><sup>opt</sup> of 1.55 eV and a HOMO level of −4.97 eV. GPC revealed that <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT</strong> has a higher molar mass (3634 Da) relative to <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong> (3105 Da). XRD studied verified that fluorinating the benzothiadiazole acceptor moiety improves molecular ordering by slightly promoting the π-π stacking distances of <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong> backbones in solid state. This study also offers a robust understanding of the electronic, functional, and molecular characteristics of the studied monomers using quantum chemical simulations. Computational studies based on density functional theory (DFT) with M06/6-311G* level of theory was employed to investigate the nonlinear optical (NLO) response and charge transfer properties. The optimized molecular geometry of <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong> shows reduced dihedral angles, suggesting improved charge transfer characteristics over its <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTB</strong>. The higher NLO response of <strong>DTP</strong><sub><strong>PH</strong></sub><strong>DTBT2F</strong>, with an amplitude of 2189× 10<sup>−36</sup> esu, was fou","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116641"},"PeriodicalIF":4.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144671031","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}

{"title":"Photocatalytic selective oxidation of 1-naphthol under red light using SBA-15-supported zinc phthalocyanine","authors":"Yaşar Gök ,&nbsp;Recep Erdem ,&nbsp;Halil Zeki Gök","doi":"10.1016/j.jphotochem.2025.116640","DOIUrl":"10.1016/j.jphotochem.2025.116640","url":null,"abstract":"<div><div>Naphthoquinones are important redox-active compounds with broad applications in pharmaceuticals and materials science. Their sustainable synthesis via photocatalytic oxidation of naphthols has attracted increasing attention due to its environmental compatibility. In this study, a zinc phthalocyanine-functionalized mesoporous silica material (SBA-15-ZnPc) was synthesized and evaluated as a heterogeneous photocatalyst for the visible-light-driven oxidation of 1-naphthol to 1,4-naphthoquinone. The photocatalyst was prepared by covalently anchoring hydrobenzoin-substituted ZnPc onto chloropropyl-functionalized SBA-15. Characterization by FT-IR, solid-state UV–Vis, TGA, SEM, TEM, BET, and XRD confirmed successful immobilization and structural integrity. SBA-15-ZnPc exhibited strong absorption at 683 nm and a narrow band gap, enabling efficient activation under red LED light. Photocatalytic tests demonstrated excellent activity, selectivity (&gt;95 %), and reusability in air at room temperature. Under optimized conditions, a 97.7 % conversion was achieved in 15 min. No leaching of ZnPc was detected after multiple cycles. Compared to other reported systems, SBA-15-ZnPc showed superior efficiency, stability, and sustainability. These results highlight the potential of ZnPc-anchored mesoporous materials as practical photocatalysts for green oxidative transformations under mild conditions.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116640"},"PeriodicalIF":4.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144671032","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}

{"title":"Understanding the effect of using metal oxide as photoanode modification on the selectivity of brine oxidation","authors":"Hitoshi Kusama,&nbsp;Kazuhiro Sayama","doi":"10.1016/j.jphotochem.2025.116618","DOIUrl":"10.1016/j.jphotochem.2025.116618","url":null,"abstract":"<div><div>Recently, we considerably enhanced the Faraday efficiency (FE) for O₂ evolution (FE(O₂)) (without Cl₂ production) through photoelectrochemical brine oxidation using the Mn-oxide-loaded BiVO₄/WO₃/FTO (FTO = F-doped SnO₂ conductive glass) photoanode under light irradiation (Sayama, et al. 2020). Herein, using density functional theory with small-cluster models of metal oxides, we elucidate the mechanism by which Mn oxide modification promotes oxygen evolution reaction (OER) while suppressing chlorine production reaction (CPR) compared to Fe, Ni, and Co oxides. OER involving two H₂O molecules proceeds via four proton-coupled electron transfer (PCET) steps featuring peroxide intermediates, while CPR involving two HCl molecules proceeds via two PCET steps. Based on the free-energy change of the rate-limiting step (Δ<em>G</em>_RLS), i.e., the step requiring the highest energy, and difference in the Δ<em>G</em>_RLS values for OER and CPR (Δ<em>G</em>_RLS(OER) − Δ<em>G</em>_RLS(CPR)), OER efficiency relative to CPR increases with metal oxide modification in the order of Co &lt; Ni &lt; Fe &lt; Mn oxides. This trend is consistent with the observed decreasing order for FE(Cl₂) and increasing order for FE(O₂). Thus, our computational approach incorporating the small-cluster approximation can reproduce the experimental trends for OER and CPR when using some metal-oxide-modified photoanodes as well as anodes. This result verifies that Mn oxide functions as an electrocatalyst for O₂ evolution.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116618"},"PeriodicalIF":4.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144671029","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}

{"title":"Design of a Hollow MnFe2O4@C@Graphdiyne Heterostructure for enhanced visible-light Photocatalysis of tetracycline hydrochloride","authors":"Ying Han ,&nbsp;Xiangyu Li ,&nbsp;Ning Fu ,&nbsp;Jie He ,&nbsp;Xingang Li ,&nbsp;Guixiang Teng ,&nbsp;Chun Zhang","doi":"10.1016/j.jphotochem.2025.116644","DOIUrl":"10.1016/j.jphotochem.2025.116644","url":null,"abstract":"<div><div>Reating hollow-structured materials is a smart strategy for fine-tuning photocatalyst performance. These hollow designs significantly improve photocatalytic activity by maximizing light capture, thereby enhancing the material's ability to absorb photons. The unique architecture essentially acts like a light trap, making the catalyst far more efficient at harnessing solar energy. In this study, a hollow mesoporous MnFe₂O₄@C@Graphdiyne (HMCGs) photocatalyst was successfully synthesized for photocatalytic reactions under visible light irradiation. The synthesis of this photocatalytic material was achieved using a two-phase interface method. Both ferrite and graphdiyne are non-toxic materials, and graphdiyne features a tunable band gap. This innovative hollow composite catalyst, crafted from advanced materials, exhibits dual functionality—harnessing both photocatalytic and redox capabilities. These synergistic properties prove essential for efficiently breaking down organic contaminants in wastewater, ensuring both environmental safety and optimal performance. The synergistic effect of the interface interaction between graphdiyne (GDY) and hollow mesoporous carbon (HMC) improved the degradation efficiency of HMCGs photocatalyst to 89 % after 90 min, which is much higher than that of the original MnFe₂O₄ (52.1 %) and HMC (60.8 %). The rational design of the hollow mesoporous HMCGs photocatalyst demonstrates excellent adaptability and stability. Consequently, the multiple reactive oxygen species (ROS) generation pathways exhibited remarkable degradation performance. The results of this project are anticipated to provide a strong basis for the future advancement of effective catalysts in the treatment of organic wastewater.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116644"},"PeriodicalIF":4.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144686863","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}

{"title":"Enhanced piezo-photocatalytic performances of visible-light-driven CdIn2S4/SrBi2Ta2O9 S-scheme heterojunction through ferroelectric polarization effect","authors":"Yan Yan ,&nbsp;Zeping Rao ,&nbsp;Wei Cai ,&nbsp;Xue Yang ,&nbsp;Zhenhua Wang ,&nbsp;Rongli Gao ,&nbsp;Gang Chen ,&nbsp;Xiaoling Deng ,&nbsp;Chunlin Fu","doi":"10.1016/j.jphotochem.2025.116646","DOIUrl":"10.1016/j.jphotochem.2025.116646","url":null,"abstract":"<div><div>Piezo-photocatalytic technology is an advanced oxidation process that combines photocatalysis with piezoelectric catalysis. The core concept involves constructing a catalyst composite system that effectively synergizes light and electric fields. In this study, a novel S-scheme piezo-photocatalytic heterojunction with high catalytic activity was successfully constructed using SrBi₂Ta₂O₉ (SBTO), a bismuth-layered Aurivillius phase ferroelectric material, and CdIn₂S₄ (CIS), which has a narrow bandgap. Notably, the photocatalytic efficiency of the S-scheme CIS/SBTO (10 % CIS/SBTO) heterojunction is 6.5 times higher than that of individual CIS and 1.4 times higher than that of individual SBTO, demonstrating a significant enhancement in photocatalytic activity. This enhancement is attributed to the interfacial electric field of the S-scheme heterojunction, which facilitates the effective separation of photogenerated electron-hole pairs and enables the potential to drive redox reactions for photocatalysis. Furthermore, corona poling further enhanced the ferroelectric polarization and piezoelectric response of the CIS/SBTO composite. Based on this, the interfacial charge transfer and degradation mechanisms of the S-scheme CIS/SBTO heterojunction are elucidated, offering a successful example for designing efficient piezo-photocatalytic systems using SBTO.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116646"},"PeriodicalIF":4.1,"publicationDate":"2025-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144665813","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}

{"title":"High quantum efficiency achieved in novel multifunctional far-red-emitting LaLi0.333Ti0.667O3: Mn4+ double perovskite phosphor","authors":"Yue Zhong ,&nbsp;Yang Li ,&nbsp;Tao Su ,&nbsp;Jing Xie ,&nbsp;Xianze Li ,&nbsp;Wenming Wang ,&nbsp;Yan Pan ,&nbsp;Xiantao Wei ,&nbsp;Yong Li","doi":"10.1016/j.jphotochem.2025.116632","DOIUrl":"10.1016/j.jphotochem.2025.116632","url":null,"abstract":"<div><div>The advancement of modern artificial plant cultivation necessitates the development of high-performance red-light sources precisely tailored to plant spectral absorption profiles. Such sources are crucial for improving crop yield and quality in contemporary agricultural practices. In this study, a far-red-emitting double perovskite phosphor LaLi_0.333Ti_0.667O₃: Mn⁴⁺ was successfully synthesized via a facile solid-state reaction method. Systematic investigations were conducted on the crystal structure, luminescent properties, and decay characteristics of the phosphor. Under 355 nm excitation, the optimized LaLi_0.333Ti_0.667O₃: 0.3 mol% Mn⁴⁺ phosphor demonstrates a prominent far-red emission peak at 726 nm, along with exceptional thermal stability, retaining 48.7 % of its room-temperature intensity at 420 K. Thermal quenching analysis yielded an activation energy (ΔE) of 0.388 eV. Remarkably, this phosphor achieves an ultrahigh internal quantum yield (QY) of 47 % within the 650–850 nm spectral range. The fabricated phosphor-converted light emitting diode (pc-LED) device exhibits precise spectral congruence with phytochrome far-red (P_fr) absorption (730 nm), indicating significant potential for photomorphogenetic regulation in agricultural applications through supplementary lighting strategies. Furthermore, due to its superior tissue penetration capability, this phosphor also shows promise for applications in non-invasive medical diagnostics.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116632"},"PeriodicalIF":4.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144655853","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}

{"title":"Keto–enol tautomerism modulates the photoluminescent sensing of ketones by terpyridine derivatives","authors":"Marlene Vargas-Zamarripa ,&nbsp;Jorge Molina González ,&nbsp;Osvaldo Carreño-Vega ,&nbsp;Erik Díaz Cervantes ,&nbsp;Oracio Serrano ,&nbsp;Gonzalo Ramírez García","doi":"10.1016/j.jphotochem.2025.116636","DOIUrl":"10.1016/j.jphotochem.2025.116636","url":null,"abstract":"<div><div>Ketones are versatile organic compounds involved in various natural and industrial processes. Therefore, developing practical methods for their detection is essential for applications in industrial safety, food quality control, and environmental monitoring. This work reports a novel and fundamental method for the photoluminescent sensing of ketones with terpyridine derivatives. Firstly, 4′-(4-<em>N</em>-aminoethylenephenyl)-2,2′:6′,2″-terpyridine (TpyPhEDA) was synthesized, and a comprehensive study of its structural and photoluminescent properties was conducted, emphasizing its application as a sensor. The luminescent response was evaluated in various organic solvents and ketones of different chemical nature, revealing a highly selective reaction with acetylacetone (AcAc). The analytical response was characterized by rapid reaction kinetics, enhanced emission intensity, band broadening, emission lifetime shortening, and a shift in the emission wavelengths as AcAc concentration increased. The underlying sensing mechanism involves a Schiff base formation between TpyPhEDA and AcAc, governed by a keto-enamine tautomeric form. The resulting Schiff base is stabilized in its keto-enamine form, enabling molecular polarization, as demonstrated by molecular electrostatic potential surface (MEPS) diagrams. This polarization triggers intramolecular charge transfer (ICT) processes, leading to turn-on luminescence and wavelength-shifting dual-mode detection of AcAc. Those results demonstrate that keto-enol tautomerism plays a crucial role in modulating the sensor's photoluminescent response, explaining variations in reaction kinetics and providing the basis for selective sensing of ketones.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116636"},"PeriodicalIF":4.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144680591","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}

{"title":"Enhanced photocatalytic degradation of LOMH by CNTs/COF composite under LED light irradiation","authors":"Xueyi Xie ,&nbsp;Wei Liu ,&nbsp;Jin Zhang ,&nbsp;Yuanting Deng","doi":"10.1016/j.jphotochem.2025.116633","DOIUrl":"10.1016/j.jphotochem.2025.116633","url":null,"abstract":"<div><div>In this work, CNTs/COF composite photocatalyst was successfully synthesized and its structure, morphology, and optical properties were characterized. The photocatalytic performance of the CNTs/COF composite was evaluated by degrading lomefloxacin hydrochloride (LOMH) under LED illumination. The results revealed that incorporating CNTs significantly enhanced the light absorption capability, promoted the separation of photogenerated carriers, and improved photocatalytic efficiency. Through the synergistic action of persulfate (PS), a degradation efficiency of 75.29 % was achieved, with an apparent rate constant 6.53 times higher than that of pure COF. Furthermore, active species trapping experiments and electron spin resonance (ESR) analysis indicated that singlet oxygen (¹O₂) and superoxide radicals (•O₂⁻) were the dominant reactive species. Work function analysis further confirmed the efficient electron transfer between the COF and CNTs. This study proposes an energy-efficient strategy for removing antibiotic pollutants under low-energy LED light, demonstrating a promising application potential.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116633"},"PeriodicalIF":4.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663287","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}

{"title":"Synthesis, Photophysics, and DPPH assays of novel luminescent N-Thiocarbamoyl Pyrenyl Pyrazolines","authors":"Douglas H.C. Bughi ,&nbsp;Yasmin L. Santos ,&nbsp;Guilherme C. Paveglio ,&nbsp;Sidnei M. Silva ,&nbsp;Luiz A.S. Costa ,&nbsp;Bernardo A. Iglesias ,&nbsp;Gleison A. Casagrande ,&nbsp;Lucas Pizzuti","doi":"10.1016/j.jphotochem.2025.116634","DOIUrl":"10.1016/j.jphotochem.2025.116634","url":null,"abstract":"<div><div>This work reports the synthesis, structural characterization, photophysical properties, DPPH radical scavenging efficiency, and computational analysis (DFT) of novel luminescent <em>N</em>-thiocarbamoyl pyrenyl pyrazolines. The pyrenyl chalcone intermediates were synthesized in 50–80 % yield via Claisen-Schmidt condensation of 1-acetylpyrene with <em>para</em>-substituted aromatic aldehydes under basic conditions. Subsequent cyclocondensation with thiosemicarbazide afforded the target 3-pyrenylpyrazoline derivatives in 55–75 % yield. All pyrazolines exhibited intense luminescence in the 450–500 nm range in solution and at 500–600 nm in the solid state, with fluorescence lifetimes ranging from 2.90 ± 0.82 to 3.55 ± 0.95 ns, which is attributed to electronic transitions localized on the pyrene moiety. Aggregation-induced emission (AIE) was observed, likely due to π-stacking interactions facilitating aggregate formation. DFT calculations corroborated experimental UV–Vis absorption spectra, revealing that the primary electronic transitions involve HOMO-LUMO excitations from the thiocarbamoyl group to the pyrene core. Additionally, the compounds demonstrated significant antioxidant activity in DPPH assays, with derivative <strong>5b</strong> (R = OMe) exhibiting highest radical scavenging efficiency, comparable to ascorbic acid and resveratrol standards.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116634"},"PeriodicalIF":4.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663365","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}

{"title":"Sulfur under pressure and laser irradiation: Effect of nanoconfinement","authors":"Shuanglong Chen ,&nbsp;Jianwen Wang ,&nbsp;Zhen Zhen ,&nbsp;Xin Li ,&nbsp;Yifeng Jiang ,&nbsp;Lv Hang ,&nbsp;Qiushi Wang ,&nbsp;Enlai Dong","doi":"10.1016/j.jphotochem.2025.116631","DOIUrl":"10.1016/j.jphotochem.2025.116631","url":null,"abstract":"<div><div>Unlike bulk materials, nanomaterials usually exhibit differences in their structures and properties. In this paper, we have performed a comparative investigation on the pressure- and laser-induced responses of sulfur in its bulk state and nano state which is confined in nanopores of CMK-3. In Raman study, the influences of laser irradiation and nanoconfinement on the pressure-induced structural evolutions and the reversibilities of sulfur have been discussed. Under high pressure, sufficient laser irradiation with high power density facilitates the transformation of bulk sulfur into a crystalline phase rather than an amorphous state. In the nanospaces of CMK-3, S<img>I phase with deformed S₈ rings amorphizes or transforms to S-II at lower pressures and then further transformations to high pressure phases (S-VI, S-III) are delayed due to the nanoconfinement effect. Upon decompression from the amorphous state, the confined sulfur exhibits a greater tendency to revert back to ring-like structures. However, once the high pressure phases with spiral chains are formed under high pressures, chain-like structures become dominant in the released samples. In X-ray diffraction (XRD) study, it is possible that orthorhombic S<img>I phase undergoes a pressure-induced isostructural transformation in both bulk and confined states. This transformation completes at around 12 GPa, accompanied by reorientation or ordering of S₈ rings. The compressibility of sulfur confined in CMK-3 is suppressed in the <em>ab</em>-plane due to spatial constraints, whereas a slight enhancement is observed along the <em>c</em>-axis. This abnormal compressible behavior leads to a 38.7 % increase in the bulk modulus of the confined sulfur. This study not only sheds new light on the pressure- and photo-induced behaviors of the confined sulfur species, but also expands the phase diagram of sulfur under external stimuli to the nanoscale regime and demonstrates the applicability of sulfur filled CMK-3 (S@CMK-3) composites in the field of functionalized lithium‑sulfur (Li<img>S) batteries under external pressure and irradiation stimuli.</div></div>","PeriodicalId":16782,"journal":{"name":"Journal of Photochemistry and Photobiology A-chemistry","volume":"470 ","pages":"Article 116631"},"PeriodicalIF":4.1,"publicationDate":"2025-07-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144663286","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}