Article
Chemistry, Physical
Renli Chen, Shenlong Jiang, Qun Zhang, Yi Luo
Summary: A mechanistic study of a PTCDA2-/TiO2 dye-sensitized photocatalytic system reveals a vibrationally excited-state-selective, visible-light photo-catalytic hydrogen evolution reaction. An intermediate complex (IC) state with a lifetime of about 12 ps mediates the interfacial electron transfer (IET) channel from a specific excited state of PTCDA2- to the conduction band continuum of TiO2.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Yusef R. Farah, Amber T. Krummel
Summary: The electronic structure of the N3/TiO2 interface has a direct impact on the performance of dye sensitized solar cells. This study found that significant changes occur in the dye's orientation at pH ≤ 2.0, resulting in a change in the interfacial electronic structure that hinders electron transfer.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Jiao Li, Haoran Liang, Yuanbiao Li, Jiao Shi
Summary: Researchers have developed a semi-artificial photoanode system by modifying the surface of a conducting electrode with photosystem II (PSII). This system shows significantly improved photocurrent response and stable electron transfer capabilities. The enhancement is attributed to the modified electrode surface and the three-dimensional microstructure of a V2O5/TiO2 composite, which promote protein immobilization and facilitate cascaded electron transfer. This work could pave the way for advanced solar energy conversion systems utilizing photoactive PSII combined with artificial metal oxides and other semiconductor nanomaterials.
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
(2023)
Article
Chemistry, Physical
Fan Tian, Jin Chen, Fengxi Chen, Yunling Liu, Yongqing Xu, Rong Chen
Summary: This study developed a benzyl thiol protected nickel nanocluster as a co-catalyst for photocatalytic hydrogen evolution over TiO2 catalyst, achieving a thirty times enhancement of hydrogen evolution efficiency by depositing the nanocluster on the TiO2 surface. The presence of visible light could not solely simulate catalytic activity, but it could promote the hydrogen evolution efficiency of Ni-6/TiO2 under ultraviolet irradiation.
APPLIED CATALYSIS B-ENVIRONMENTAL
(2021)
Article
Chemistry, Multidisciplinary
Claudio Imparato, Gerardino D'Errico, Wojciech Macyk, Marcin Kobielusz, Giuseppe Vitiello, Antonio Aronne
Summary: Metal oxide-organic hybrid semiconductors have specific properties determined not only by their composition but also by the synthesis procedure and functionalization method. This study presents a sol-gel route as an alternative strategy to synthesize titanium oxide-based materials containing organic molecules coordinated to the metal. The effect of ligand molecular structure on the surface properties of the hybrids is investigated.
Article
Optics
Yuchen Dai, Pengfei Qi, Guangyi Tao, Guangjie Yao, Beibei Shi, Zhixin Liu, Zhengchang Liu, Xiao He, Pu Peng, Zhibo Dang, Liheng Zheng, Tianhao Zhang, Yongji Gong, Yan Guan, Kaihui Liu, Zheyu Fang
Summary: This letter investigates phonon-assisted photon upconversion (UPC) in twisted 2D semiconductors, where an inverted contrast between UPC and conventional photoluminescence (PL) of WSe2 twisted bilayer emerges. A 4-fold UPC enhancement is achieved in the 5.5 degrees twisted bilayer while PL weakens by half. The rotation-angle-dependent UPC enhancement is attributed to reduced interlayer exciton conversion efficiency driven by lattice relaxation and enhanced pump efficiency resulting from spectral redshift. This counterintuitive phenomenon provides a novel insight into the effect of twisted angle on UPC and light-matter interactions in 2D semiconductors. Furthermore, the UPC enhancement platform with various superimposable means offers an effective method for lighting bilayers and expanding the application prospect of 2D stacked van der Waals devices.
LIGHT-SCIENCE & APPLICATIONS
(2023)
Article
Chemistry, Physical
Bhagyashree Mahesha Sachith, Takuya Okamoto, Sushant Ghimire, Tomokazu Umeyama, Yuta Takano, Hiroshi Imahori, Vasudevanpillai Biju
Summary: This study reveals the distance-dependent and diffusion-controlled interfacial electron transfer across perovskite-electron acceptor heterojunction films. Perovskite nanocrystals exhibit long-range carrier migration in self-assembled films, while acceptors quench photoluminescence intensity without affecting lifetime. The research underscores the importance of interfacial electron transfer in perovskite films.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Chemistry, Physical
Suping Jia, Hao Wang, Tong Cheng, Huinian Zhang, Huiqi Wang, Chaorui Xue, Shengliang Hu
Summary: This study presents a simple and practical method to passivate the surface defects of TiO2 nanoparticles. The modified TiO2 enhances the growth and crystallization of FAMA perovskite film and improves the electron extraction and suppresses charge recombination at the perovskite-TiO2 interface. The modified TiO2-based perovskite solar cells exhibit a high power conversion efficiency of 20.27% and improved stability.
JOURNAL OF ALLOYS AND COMPOUNDS
(2022)
Article
Optics
Lijie Wang, Tsz Him Chow, Malte Oppermann, Jianfang Wang, Majed Chergui
Summary: We report on the deep-to-near-UV transient absorption spectra of Au/SiO2 and Au/TiO2 core-shell nanoparticles (NPs) and UV-excited bare anatase TiO2 NPs. The presence of electrons/holes in the conduction/valence band of the material is indicated by the bleaching of the first excitonic transition of anatase TiO2 at -3.8 eV. Two-photon excitation does not occur in bare TiO2 NPs, but takes place in the TiO2 shell of Au/TiO2 core-shell NPs due to plasmon resonance enhancement. The bleach of the 3.8 eV band of TiO2 lives significantly longer in the core-shell NPs, indicating longer storage of excess electrons/holes.
PHOTONICS RESEARCH
(2023)
Article
Nanoscience & Nanotechnology
Beatriu Domingo-Tafalla, Tamal Chatterjee, Federico Franco, Javier Perez Hernandez, Eugenia Martinez-Ferrero, Pablo Ballester, Emilio Palomares
Summary: Electro- and photoinduced charge transfer in nanocrystalline mesoporous TiO2 film and TiO2/iron porphyrin hybrid films under CO2 reduction conditions were studied. The TiO2 film exhibited a reduction in the absorption and lifetime of photogenerated electrons under laser excitation and applied voltage. The TiO2/iron porphyrin films showed faster charge recombination kinetics and exclusive formation of CO during CO2 reduction. The competitive processes between oxidized iron porphyrin and TiO2 conduction band electrons were identified as the reason for the moderate performances of the hybrid films.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Inorganic & Nuclear
Josephine A. Jacob-Dolan, Matt D. Capobianco, Han-Yu Liu, Cristina Decavoli, Robert H. Crabtree, Gary W. Brudvig
Summary: This study reveals that unmodified BODIPY and its parent molecule dipyrrin can bind to TiO2 surfaces through specific functional groups, and these binding modes are more robust than previous methods, offering potential applications in (photo)catalysis.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Multidisciplinary
Dong Li, Yunxuan Zhao, Yingxuan Miao, Chao Zhou, Li-Ping Zhang, Li-Zhu Wu, Tierui Zhang
Summary: This study reports an effective strategy to enhance the performance of urea photosynthesis using TiO2-immobilized reversible single-atom copper. Reversible single-atom copper accelerates electron transfer and ensures sufficient photogenerated electrons for multi-electron-demanding co-photoactivation, resulting in high urea production rates. This strategy is of great significance for improving the photoelectron-extraction ability of photocatalysts.
ADVANCED MATERIALS
(2022)
Article
Chemistry, Physical
Xiao Zhang, Huizhong Ma, Min Zhang, Yuchen Ma
Summary: The mechanism of CO2 photoreduction under the catalysis of anatase TiO2 is still not well understood. This study reveals that interfacial charge-transfer (CT) excitons play a crucial role in the reduction reactions, simplifying the process and reducing the reaction barriers. Additionally, the study shows that the remaining holes after CO2 reduction can promote the dissociation and oxidation of H2O, further enhancing the reaction efficiency.
Article
Chemistry, Multidisciplinary
Sumit Kumar, Abha Jha, Prasenjit Kar
Summary: Hydrophobically capped formamidinium lead bromide perovskite nanocrystals exhibit bright green emission. The interfacial hole transfer phenomenon was evaluated through photoluminescence spectral studies and time-correlated single photon counting measurements. The presence of graphitic carbon nitride led to a decrease in both absolute photoluminescence quantum yield and decay lifetime value, indicating the migration of holes from the nanocrystals to g-C3N4.
NEW JOURNAL OF CHEMISTRY
(2023)
Review
Chemistry, Multidisciplinary
Zhongrui Yu, Haobo Liu, Mingyuan Zhu, Ying Li, Wenxian Li
Summary: This review provides a comprehensive overview of current research efforts towards the development of 1D TiO2-based photoelectrodes for heterogeneous PEC water splitting, discussing the influences of nanoarchitectures and energy band engineering on interfacial charge transfer and separation. Additionally, the review explores the interactions between 1D TiO2 and photoactive materials of different dimensions.
Article
Chemistry, Multidisciplinary
Nitesh Kumar, Michael J. Servis, Aurora E. Clark
Summary: This study examines the speciation of uranyl at the liquid/liquid interface using classical molecular dynamics simulations. The interactions of uranyl with nitrate exhibit variability that prevents dehydration at the interface, while Li+ loses solvation water in the interfacial region. Despite significant perturbations in ion-ion interactions and solvation dynamics, the association constants of uranyl with nitrate remain unchanged, allowing for the prediction of the distribution of interfacial uranyl nitrate complexes.
SOLVENT EXTRACTION AND ION EXCHANGE
(2022)
Article
Chemistry, Physical
Ernest R. Davidson, Aurora E. Clark
Summary: Population analyses are crucial for computational chemists, particularly when dealing with partitioning electron density into atomic contributions, which involves interesting philosophical choices. Historical context significantly influences common conceptions of chemical bonding and reactivity. This work reviews aspects of orbital and spatial decomposition schemes of the density matrix.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2022)
Article
Chemistry, Physical
Michael J. Servis, Biswajit Sadhu, L. Soderholm, Aurora E. Clark
Summary: This study investigates the impact of dipole-dipole interactions and molecular structure on the morphology of amphiphile assemblies. The research demonstrates that appropriate conformational sampling significantly influences the self-assembly of malonamide-based amphiphiles. Quantitative analysis reveals that dipole alignment and alkyl tail sterics play crucial roles in determining the structure of aggregates, with dipole alignment promoting linear patterns of intermolecular interactions within aggregates.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Physical
Simon Nussbaum, Etienne Socie, Liang Yao, Jun-Ho Yum, Jacques-E Moser, Kevin Sivula
Summary: This study reports the preparation and incorporation of asymmetric naphthalenediimide (NDI) spacer chromophore cations with different amine-bearing alkyl linker chains into thin films of layered hybrid organic-inorganic perovskite (LHOIP) materials. In situ UV-vis spectroscopic kinetic studies reveal that shorter linker chain lengths require higher annealing temperatures to form the LHOIP structure. Avrami analysis of the layered perovskite formation demonstrates an evolution from three-dimensional to quasi-two-dimensional crystal growth with increasing linker chain length.
CHEMISTRY OF MATERIALS
(2022)
Article
Chemistry, Physical
Hung M. Le, Sushant Kumar, Nathan May, Ernesto Martinez-Baez, Ravishankar Sundararaman, Bala Krishnamoorthy, Aurora E. Clark
Summary: Identifying collective variables (CVs) for chemical reactions is crucial but challenging due to the nonmeaningful motions of bulk solvent. This work proposes a distance-attenuated projection method that enables both PCA and UMAP to accurately identify CVs in the presence of explicit solvent and determine the specific importance of solvent molecules in chemical reactions.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2022)
Article
Chemistry, Physical
Biswajit Sadhu, Aurora E. Clark
Summary: In non-polar media, polar co-solutes enhance the self-assembly of amphiphiles. This study investigates the individual effects of water and nitric acid on the self-assembly of TODGA and reveals that water promotes local aggregation while inhibiting the formation of large water clusters, while nitric acid disrupts the water hydrogen bond network and encourages local aggregation.
JOURNAL OF MOLECULAR LIQUIDS
(2022)
Article
Chemistry, Physical
Marie Bischoff, Na Yeon Kim, Ji Bong Joo, Arianna Marchioro
Summary: This study demonstrates the use of polarimetric angle-resolved second harmonic scattering (AR-SHS) as an all-optical, label-free probe for colloid surface pKa values. By measuring dispersions of 100 nm anatase TiO2 particles, the researchers successfully extracted surface potential and surface susceptibility, and evaluated the surface pKa values.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Bingxin Chu, Arianna Marchioro, Sylvie Roke
Summary: Polarimetric angle-resolved second-harmonic scattering (AR-SHS) is used to study unlabeled interfaces of nano-sized particles in aqueous solutions. The AR-SHS patterns provide information about the electrical double layer structure. In this study, the size dependence of surface and electrostatic geometric form factors for nonlinear scattering and their contribution to AR-SHS patterns are calculated.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Letter
Chemistry, Multidisciplinary
Arianna Marchioro, Thaddeus W. Golbek, Adam S. Chatterley, Tobias Weidner, Sylvie Roke
COMMUNICATIONS CHEMISTRY
(2023)
Article
Chemistry, Physical
George C. Fish, Aaron T. Terpstra, Algirdas Ducinskas, Masaud Almalki, Loi C. Carbone, Lukas Pfeifer, Michael Gratzel, Jacques-E. Moser, Jovana V. Milic
Summary: Organic materials can modify the optical properties of layered (2D) hybrid perovskites, and their effects on photophysics are often overlooked. In this study, the impact of spacer size and perovskite phase configuration on charge transfer excitons in 2D perovskites is investigated using transient absorption spectroscopy and electroabsorption spectroscopy. It is found that charge transfer excitons form in the Dion-Jacobson (DJ) phase, leading to a photoinduced Stark effect dependent on the spacer size. Moreover, temperature-dependent measurements reveal new features in the transient spectra of the Ruddlesden-Popper (RP) phase at low temperatures due to the quantum-confined Stark effect.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Bingxin Chu, Denys Biriukov, Marie Bischoff, Milan Predota, Sylvie Roke, Arianna Marchioro
Summary: We investigated the structure of the electrical double layer (EDL) in SiO2 nanoparticle suspensions and its evolution with increasing ionic concentration using angle-resolved second harmonic scattering (AR-SHS). We characterized the inner-sphere adsorption, diffuse layer formation, and outer-sphere adsorption below millimolar salt concentrations. Additionally, we discovered a decrease in surface potential and compression in the EDL thickness at millimolar salt concentrations.
FARADAY DISCUSSIONS
(2023)
Article
Chemistry, Multidisciplinary
Simon Nussbaum, Etienne Socie, George C. Fish, Nicolas J. Diercks, Hannes Hempel, Dennis Friedrich, Jacques-E. Moser, Jun-Ho Yum, Kevin Sivula
Summary: Incorporating organic semiconducting spacer cations into layered lead halide perovskite structures can mitigate dielectric and quantum confinement effects by inducing charge-transfer between the organic and inorganic layers. This study reports the synthesis and characterization of novel DJ-phase organic-inorganic layered perovskite semiconductors with a naphthalene diimide (NDI) based spacer cation that can accept photogenerated electrons from the inorganic layer. The NDI-based thin film with a 6-carbon alkyl chain length exhibited high electron mobility and trap passivation by the NDI spacer cation.
Article
Chemistry, Physical
William Smith, Maxime Pouvreau, Kevin Rosso, Aurora E. Clark
Summary: pH dependent interfacial chemistry is influenced by the distribution and pK(a) values of different surface active sites. Recent advancements in synthesizing nanoparticles of various minerals offer an opportunity to reinterpret interfacial properties and reactivity.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
George C. Fish, Juan Manuel Moreno-Naranjo, Andreas Billion, Daniel Kratzert, Erwin Hack, Ingo Krossing, Frank Nuesch, Jacques-E Moser
Summary: The study demonstrates that a decrease in H-aggregation in organic salt semiconductors leads to reduced charge transfer, however, carrier mobility remains largely unchanged as a decrease in energetic disorder helps alleviate trapping of charges by H-aggregates.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Zhu Liu, Aurora E. Clark
Summary: Using molecular dynamics and other methods, this study reveals an elegant mechanism for the transport of water across water/octanol phase boundaries. The mechanism involves the formation of a semi-organized bilayer island and is driven by the differential free energies of solvation of H2O across the interface.