Melisande Kost, Jean Felix Dushimineza, Knut Müller-Caspary, Thomas Bein
{"title":"Optimized Oxidation Temperature Enhances OER Performance of IrO₂-Loaded SnO₂ Nanofibers – Role of Charge Carrier Percolation Pathways","authors":"Melisande Kost, Jean Felix Dushimineza, Knut Müller-Caspary, Thomas Bein","doi":"10.1002/admi.202400997","DOIUrl":"10.1002/admi.202400997","url":null,"abstract":"<p>The potential for reducing iridium content in large-scale proton-exchange membrane (PEM) electrolysis is examined using a fibrous support morphology to enhance electron percolation. Focusing on high activity, stability, and conductivity, ultra-small, interconnected IrO<i><sub>x</sub></i>/IrO<sub>2</sub> nanoparticles anchored to electrospun SnO<sub>2</sub> nanofibers (IrO<i><sub>x</sub></i>/IrO<sub>2</sub>@SnO<sub>2</sub>) are investigated, with particular attention to the crystallinity of the iridium phase. Scanning transmission electron microscopy (STEM), conducted both before and after use as an electrocatalyst for the oxygen evolution reaction (OER), reveals how the oxidation temperature impacts the crystallinity and stability of the iridium oxide phase. The results suggest that further reductions in iridium content may be achieved by optimizing synthesis parameters. Here, the highest iridium utilization is achieved at an oxidation temperature of 375 °C, with improved conductivity and electrochemical activity. Transmission electron microscopy (TEM) indicates that higher oxidation temperatures result in fragmentation of conduction pathways, negatively affecting catalyst performance. Furthermore, TEM reveals the onset of IrO₂ crystallization between 365 and 375 °C, with cyclic voltammetry (CVA) emphasizing the critical role of conductivity in ensuring efficient charge carrier transport to active sites. This study not only deepens the understanding of iridium-based catalysts but also identifies practical strategies to enhance cost-effectiveness and efficiency in PEM electrolysis technologies.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202400997","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Juan Luis Fajardo-Diaz, Armando David Martinez-Iniesta, Ayaka Yamanaka, Syogo Tejima, Kazou Izu, Shigero Saito, Jun Maeda, My Ali El Khakani, Winadda Wongwiriyapan, Feng Wang, Takuya Hayashi, Kenji Takeuchi, Rodolfo Cruz-Silva, Morinobu Endo
{"title":"Advanced Water Production via Point of Use Super-Ultralow-Pressure Reverse Osmosis and Cellulose-Polyamide Thin-Film Nanocomposite Membranes","authors":"Juan Luis Fajardo-Diaz, Armando David Martinez-Iniesta, Ayaka Yamanaka, Syogo Tejima, Kazou Izu, Shigero Saito, Jun Maeda, My Ali El Khakani, Winadda Wongwiriyapan, Feng Wang, Takuya Hayashi, Kenji Takeuchi, Rodolfo Cruz-Silva, Morinobu Endo","doi":"10.1002/admi.202500318","DOIUrl":"10.1002/admi.202500318","url":null,"abstract":"<p>A novel thin-film nanocomposite reverse osmosis (RO) membrane was developed for point-of-use applications (POU-RO) at super-ultralow pressure (0.2 MPa), incorporating carboxymethylated cellulose nanofibers (CM-CNF). The CM-CNF with an increased number of oxygen-containing functional groups that positively impacts water flux, salt rejection stability, antifouling characteristics, and resistance to chlorine degradation compared to commercial RO-PA membranes. Transmission electron microscopy (TEM), combined with geodesic and skeletonized image analysis, revealed that the average thickness of the PA/CM-CNF membrane is 1050 nm corresponding to more than four leaf-like layers, significantly higher than commercial membranes, which typically show fewer than two layers. Moreover, a void-free active layer is created, providing excellent substrate coverage. Tests with CaCl<sub>2</sub> at 0.2 MPa showed 93.9% salt rejection and a water permeation rate of 0.93 m/d, doubling the performance of commercial membranes. Dynamic simulations confirmed the influence of CM-CNF on enhancing water diffusion at low pressure (0.2 MPa). POU-RO tests, conducted using a 2-inch spiral module fabricated in the laboratory, confirmed the superior performance of the CM-CNF membrane. Indeed, high recovery rates (>60%) and high permeation rates (close to 0.7 m/d) have been achieved by the membranes. This performance is twice than the commercial counterparts tested at 0.2 MPa.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500318","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Rounak Banerjee, Sai Uppala, Jan Kopaczek, Mohammed Y Sayyad, Patrick Hays, Renee Sailus, Seth Ariel Tongay
{"title":"Thermal and Magnetic Stability of van-der Waals Antiferromagnet CrOCl from the Bulk to Monolayer Limit","authors":"Rounak Banerjee, Sai Uppala, Jan Kopaczek, Mohammed Y Sayyad, Patrick Hays, Renee Sailus, Seth Ariel Tongay","doi":"10.1002/admi.202500278","DOIUrl":"10.1002/admi.202500278","url":null,"abstract":"<p>2D magnetic materials have been at the forefront of quantum materials research owing to their attractive and exotic magnetic properties. However, most known examples of 2D magnets have low environmental and thermal stability, posing a significant challenge to their eventual device integration. This work reports on the thermal stability of a recently discovered environmentally stable transition metal oxyhalide, CrOCl. Using differential scanning calorimetry, thermogravimetric analysis, and temperature-dependent X-ray diffraction, the studies show that van der Waals (vdW) layers of CrOCl exhibit remarkable thermal stability, significantly surpassing the temperature requirements for CMOS technology. CrOCl undergoes a two-step decomposition process, transforming into amorphous Cr<sub>2</sub>O<sub>3</sub> at ≈620 °C by releasing chlorine from its surface. Additionally, thickness-dependent thermal stability studies show no significant decrease in decomposition temperature, dropping from 630 °C in the bulk material to 550 °C in few-layer samples and down to 500 °C in the monolayer. Further, comprehensive magnetization studies indicate that despite a reduction in overall magnetization, key magnetic properties such as saturation magnetization and spin-flip behavior are retained even after extreme thermal stress. These findings offer the first insights into the thermal stability of these transition metal oxychlorides as potential candidates for robust magnetic devices requiring 2D vdW magnets.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500278","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740182","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Chemical Intercalant Affects the Structural Properties and Aqueous Stability of V2CTx MXene","authors":"Reagan A. Beers, Dijia Bao, Jessica R. Ray","doi":"10.1002/admi.202500145","DOIUrl":"10.1002/admi.202500145","url":null,"abstract":"<p>Vanadium carbide (V<sub>2</sub>CT<sub>x</sub>) MXene is a 2D nanomaterial widely investigated for energy storage applications due to its superior electrochemical properties. However, V<sub>2</sub>CT<sub>x</sub> quickly degrades in water, which limits its performance and longevity. Furthermore, the relationship between V<sub>2</sub>CT<sub>x</sub> MXene synthesis parameters and their corresponding aqueous stability is underexplored. In this study, delaminated V<sub>2</sub>CT<sub>x</sub> MXene films synthesized with four tetraalkylammonium hydroxide intercalants were characterized for their structural and aqueous stability differences. Delaminated V<sub>2</sub>CT<sub>x</sub> MXene d-spacing, flake edge lengths, and surface morphology were generally dependent on the intercalant radius. Specifically, the intercalant radius exhibited a positive correlation with d-spacing and a negative correlation with flake edge lengths. These structural differences have direct impacts on the aqueous stability of V<sub>2</sub>CT<sub>x</sub>. For example, Raman spectra of each thin film indicated that amorphous carbon formation upon water exposure positively corresponded with flake edge lengths. 3D printed film holders were fashioned to mimic electrochemical cell configurations to evaluate vanadium dissolution from each film when exposed to water. Vanadium dissolution from each film was statistically similar (i.e., no correlation with intercalant radius) and substantial (i.e., ppm concentration range). These findings will benefit aqueous applications of V<sub>2</sub>CT<sub>x</sub> MXenes, where material degradation and vanadium release may impact MXene performance.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500145","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jonathan Diederich, Agnieszka Paszuk, Isaac Azahel Ruiz Alvarado, Marvin Krenz, Mohammad Amin Zare Pour, Diwakar Suresh Babu, Jennifer Velazquez Rojas, Christian Höhn, Yuying Gao, Klaus Schwarzburg, David Ostheimer, Rainer Eichberger, Wolf Gero Schmidt, Thomas Hannappel, Roel van de Krol, Dennis Friedrich
{"title":"Ultrafast Electron Dynamics at the Water-Modified InP(100) Surface","authors":"Jonathan Diederich, Agnieszka Paszuk, Isaac Azahel Ruiz Alvarado, Marvin Krenz, Mohammad Amin Zare Pour, Diwakar Suresh Babu, Jennifer Velazquez Rojas, Christian Höhn, Yuying Gao, Klaus Schwarzburg, David Ostheimer, Rainer Eichberger, Wolf Gero Schmidt, Thomas Hannappel, Roel van de Krol, Dennis Friedrich","doi":"10.1002/admi.202500463","DOIUrl":"10.1002/admi.202500463","url":null,"abstract":"<p>The interaction of water molecules with semiconductor surfaces is relevant to various optoelectronic phenomena and physicochemical processes. Despite advances in fundamental understanding of water-exposed surfaces, the detailed time- and energy-resolved behavior of excited electrons remains largely unexplored. Here, the effects of water exposure on the near-surface electron dynamics of phosphorus-terminated p(2×2)/c(4×2)-reconstructed indium phosphide (100) (P-rich InP) are studied experimentally and matched to theoretical calculations. The P-rich InP surface, consisting of H-passivated P-dimers, serves as a model for other P-containing III-V semiconductors such as gallium phosphide (GaP) or aluminum indium phosphide (AlInP). Electron dynamics near the surface are probed with femtosecond resolution using time-resolved two-photon photoemission (tr-2PPE), a pump-probe spectroscopic technique. Pulsed water exposure preserves electronic states and significantly increases lifetimes at the conduction band minimum (CBM). Density-functional theory (DFT) calculations attribute these findings to suppression of surface vibrational modes in the top P-layer by water exposure, reducing electronic transition probabilities of near-band-gap surface states. The results suggest that many near-surface state lifetimes reported in ultra-high vacuum may change significantly upon electrolyte exposure. These states may thus contribute more strongly to surface reactions than traditionally assumed. Demonstrating this effect for the technologically relevant P-rich InP surface opens new opportunities in this underexplored area of surface electrochemistry.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 16","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500463","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nazish Saleem Abbas, Muhammad Haris Jamil, Nayab Ariff, Hamid Sharif, Peiguang Yan
{"title":"Emerging Trends of MXene Nanocomposites in Textile Substrates for Enhanced EMI Shielding: A Systematic Review","authors":"Nazish Saleem Abbas, Muhammad Haris Jamil, Nayab Ariff, Hamid Sharif, Peiguang Yan","doi":"10.1002/admi.202500484","DOIUrl":"10.1002/admi.202500484","url":null,"abstract":"<p>Electromagnetic interference (EMI) shielding represents a critical technological challenge demanding innovative materials with superior performance characteristics. This comprehensive review systematically explores MXene nanomaterials as a transformative EMI shielding solution, critically analyzing traditional nanomaterial approaches and evaluating MXene's unique properties. The review comprehensively examines MXene's integration into textile substrates through advanced fabrication methodologies, including vacuum filtration, coating and dipping, spray coating, and spin coating techniques. A rigorous assessment of performance metrics encompasses electromagnetic shielding effectiveness, material thickness, electrical conductivity, mechanical properties, surface functionalization, durability, and application-specific performance characteristics. This work examines how MXenes (Ti<sub>3</sub>C<sub>2</sub>), with their exceptional conductivity and ease of textile application, can be coupled with other nanomaterials such as graphite, carbon nanotubes (CNT), polyaniline (PANI), and silver nanowires (AgNWs) to improve EMI shielding effectiveness. A comprehensive list of MXene-based hybrid nanomaterials offers materials scientists and engineers with an important reference framework for understanding and optimizing EMI shielding solutions. Finally, despite underlining MXene's enormous potential, this paper critically states existing constraints, such as nanomaterial dispersion, environmental stability, and production processes. This in-depth review not only highlights recent achievements in MXene-based textile composites but also indicates areas where more research is required to solve existing constraints and limitations.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500484","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740183","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Thabiso Kunene, Juan Pablo Vizuet, Matthew Klenk, Peter Zapol, Ksenija Glusac, Alex B. F. Martinson
{"title":"Vapor Phase Installation of CpCo(CO)2 in MOF-808","authors":"Thabiso Kunene, Juan Pablo Vizuet, Matthew Klenk, Peter Zapol, Ksenija Glusac, Alex B. F. Martinson","doi":"10.1002/admi.202500079","DOIUrl":"10.1002/admi.202500079","url":null,"abstract":"<p>Metal-organic frameworks (MOFs), including MOF-808 present an opportunity for vapor phase installation of reactive centers that may serve as uniform sites for precision catalysis. The mechanism of cobalt installation in MOF-808 through atomic layer deposition (ALD) upon CpCo(CO)<sub>2</sub> exposure is investigated through in situ FTIR spectroscopy complemented by density functional theory modeling. The role of subsequent H<sub>2</sub>O exposure in the hydrolysis of carbonyl and cyclopentadienyl ligands to complete the installation is also investigated. In situ FTIR study reveals that upon exposure of CpCo(CO)<sub>2</sub> to MOF-808 at 115 °C, a long-lived, stable intermediate is formed that presents carbonyl stretching vibrations similar to the undissociated precursor that are attributed to multiple chemisorbed carbonyl complexes. In MOF-808, cobalt species are initially absorbed near the BTC linker rather than directly on the nodes, revealing the importance of non-covalent interactions in the installation process. DFT suggests that H<sub>2</sub>O exposure promotes carbonyl elimination but leaves a cyclopentadienyl-capped cobalt that is more stable than the complete hydrolysis product. The simulations are consistent with cobalt installation in MOF-808 using CpCo(CO)<sub>2</sub> and H<sub>2</sub>O at 115 °C and further consistent with the lack of ALD thin film deposition of cobalt oxide thin films on planar supports.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500079","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Akhlak U. Mahmood, Mehedi H. Rizvi, Joseph B. Tracy, Yaroslava G. Yingling
{"title":"Agglomeration of Nanoparticles Inhibits Solvent-Driven Ligand Stripping","authors":"Akhlak U. Mahmood, Mehedi H. Rizvi, Joseph B. Tracy, Yaroslava G. Yingling","doi":"10.1002/admi.202500234","DOIUrl":"10.1002/admi.202500234","url":null,"abstract":"<p>The colloidal stability of nanoparticles (NPs) is significantly affected by complex solvent-ligand interactions, with poor solvents often inducing NP agglomeration and ligand desorption from the surface. Despite the frequent occurrence of these phenomena in post-synthetic experiments, the underlying mechanisms remain elusive. In this study, dynamic light scattering (DLS), thermogravimetric analysis (TGA), and large-scale all-atom molecular dynamics (MD) simulations are used to investigate solvent-driven oleylamine ligand removal from Fe<sub>3</sub>O<sub>4</sub> NPs. Eight experimentally relevant NP systems under replicated solvent conditions are modeled, enabling direct comparison and yielding deep insights into solvent-mediated ligand stripping with excellent agreement. These findings reveal that ethanol's ability to strip oleylamine ligands from Fe<sub>3</sub>O<sub>4</sub> NPs is impeded by NP agglomeration, where stripped and interdigitated ligands create a steric barrier, preventing solvent molecules from accessing the NP surface. This effect becomes more pronounced with increasing NP size due to the greater ligand surface density that enhances interdigitation. Moreover, the presence of a threshold concentration of the poor solvent in binary mixtures is identified, below which the maximum number of ligands can be stripped without initiating agglomeration. These insights provide a framework for optimizing solvent-mediated ligand exchange, with implications for NP applications in catalysis, energy storage, optoelectronics, and biomedical engineering.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 16","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://advanced.onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500234","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144894288","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Guanghui Yan, Gaoshan Huang, Jianjun Shi, Yi Ouyang, Xueqin Zuo, Zhihao Bao, Yongfeng Mei
{"title":"A Review on Reactor Design and Surface Modification of Atomic Layer Deposition for Functional Nanoparticles","authors":"Guanghui Yan, Gaoshan Huang, Jianjun Shi, Yi Ouyang, Xueqin Zuo, Zhihao Bao, Yongfeng Mei","doi":"10.1002/admi.202500140","DOIUrl":"10.1002/admi.202500140","url":null,"abstract":"<p>Atomic layer deposition (ALD) has emerged as a promising method for surface modification of functional nanoparticles, enabling the versatile applications in energy, catalysis, and human health. The self-limiting surface chemistry of ALD allows not only the coating of ultrathin and conformal films but also the decoration of nanoparticle surfaces with specific nanoclusters under appropriate processing conditions. In particle ALD, one of the major challenges lies in the strong cohesive force causing nanoparticle agglomerates or aggregates, which requires their homogeneous dispersion. This review provides an overview on the developments and advancements of particle ALD, covering both reactor designs and applications. The fundamentals of ALD are first reviewed, followed by the reactor designs including fluidized bed reactors, rotating bed reactors, and atmospheric-pressure continuous spatial ALD reactors. Among them, the basics of particle fluidization are concisely outlined to establish a foundation for understanding fluidized bed reactors. The advantages and disadvantages of various reactor designs are compared and analyzed. Subsequently, the applications of ALD-modified nanoparticles are reviewed, with a focus on energy, catalysis, biomedicine, and cosmetics. Finally, the progress and applications of ALD modification for functional nanoparticles are summarized, and the perspectives in the field are proposed.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500140","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Océane Boudreau, Paul Asselin, Seyed Mehrzad Sajjadinezhad, Paul-Ludovic Karsenti, Peter Moffett, Kamal Bouarab, Pierre D. Harvey
{"title":"Rationalizing the Unexpected Inefficiencies of 3D Porphyrin-MOFs as Singlet Oxygen Photosensitizers Against Botrytis cinerea","authors":"Océane Boudreau, Paul Asselin, Seyed Mehrzad Sajjadinezhad, Paul-Ludovic Karsenti, Peter Moffett, Kamal Bouarab, Pierre D. Harvey","doi":"10.1002/admi.202500315","DOIUrl":"10.1002/admi.202500315","url":null,"abstract":"<p>Porphyrin-based MOFs (PMOFs) are known to be efficient photocatalysts and singlet oxygen (<sup>1</sup>O<sub>2</sub>) photosensitizers (PS) in solution, but their application in agriculture and food protection is practically unknown. In vitro tests on <i>Botrytis cinerea</i> using the renowned PCN-222 and PCN-224 reveal modest photo-antifungal activities at the solid–gas interface when compared to their standalone tetrakis(4-carboxyphenyl)porphyrin (TCPP) linker. This in-depth study examines the direct detection of <sup>1</sup>O<sub>2</sub>(g) phosphorescence at the solid–air interface, binding of the PMOFs with the spores of <i>B. cinerea</i> by fluorescence microscopy, fluorescence quenching of the PMOFs by oxygen, and rates of exciton migration evaluated through the singlet-singlet annihilation process. The conclusion is that a significant proportion of <sup>1</sup>O<sub>2</sub> is unable to escape the porous materials before deactivation, or does so too late to then be able to reach, and that excitation migration is not efficient enough to generate significant amounts of <sup>1</sup>O<sub>2</sub> directly at the MOF surface. Given that TCPP is its own interface with the gas phase, it is not hindered by these factors, which explains its higher efficiency under these circumstances.</p>","PeriodicalId":115,"journal":{"name":"Advanced Materials Interfaces","volume":"12 14","pages":""},"PeriodicalIF":4.4,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/admi.202500315","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144740395","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}