Interfacial Complex Research Articles

Versatile and Tunable Electrical Properties of Doped Nonoxidized Graphene Using Alkali Metal Chlorides.

With the rapid development of wearable and flexible electronics, graphene has been intensively studied for the transparent, hole transport electrode layer (HTL) of field-effect transistors, light-emitting diodes, and organic photovoltaic (OPV) cells. To modulate the sheet resistance and the work function of graphene as a HTL, the surface doping is versatile while retaining high transparency. In this work, we used a chemical doping method to control the charge carrier density, band gap, and work function of graphene with minimizing the damage of the carbon network, for which metal chlorides (NaCl, KCl, and AuCl3) were used as chemical dopants. The high-quality graphene flakes were synthesized with large lateral sizes of more than 5 μm using ternary graphite intercalation compounds. Interestingly, the AuCl3-doped graphene flake film with a film thickness of about 20 nm showed the lowest reported sheet resistance of ∼249 Ω/sq with ∼75% transmittance. Furthermore, it could control the work function from 4.32 to 5.1 eV. The interfacial dipole complexes of metal cations with a low work function and the reactive radicals such as -OH were discussed to explain this result. For the practical application, an OPV device using the AuCl3-doped graphene flake film as the HTL was fabricated and it demonstrated enhanced power conversion efficiency while maintaining high optical transparency in visible light.

System-Wide Characterization of MoArf GTPase Family Proteins and Adaptor Protein MoGga1 Involved in the Development and Pathogenicity of Magnaporthe oryzae.

ADP ribosylation factor (Arf) small GTPase family members are involved in vesicle trafficking and organelle maintenance in organisms ranging from Saccharomyces cerevisiae to humans. A previous study identified Magnaporthe oryzae Arf6 (MoArf6) as one of the Arf proteins that regulates growth and conidiation in the rice blast fungus M. oryzae, but the remaining family proteins remain unknown. Here, we identified six additional Arf proteins, including MoArf1, MoArl1, MoArl3, MoArl8, MoCin4, and MoSar1, as well as their sole adaptor protein, MoGga1, and determined their shared and specific functions. We showed that the majority of these proteins exhibit positive regulatory functions, most notably, in growth. Importantly, MoArl1, MoCin4, and MoGga1 are involved in pathogenicity through the regulation of host penetration and invasive hyphal growth. MoArl1 and MoCin4 also regulate normal vesicle trafficking, and MoCin4 further controls the formation of the biotrophic interfacial complex (BIC). Moreover, we showed that Golgi-cytoplasm cycling of MoArl1 is required for its function. Finally, we demonstrated that interactions between MoArf1 and MoArl1 with MoGga1 are important for Golgi localization and pathogenicity. Collectively, our findings revealed the shared and specific functions of Arf family members in M. oryzae and shed light on how these proteins function through conserved mechanisms to govern growth, transport, and virulence of the blast fungus.IMPORTANCEMagnaporthe oryzae is the causal agent of rice blast, representing the most devastating diseases of rice worldwide, which results in losses of amounts of rice that could feed more than 60 million people each year. Arf (ADP ribosylation factor) small GTPase family proteins are involved in vesicle trafficking and organelle maintenance in eukaryotic cells. To investigate the function of Arf family proteins in M. oryzae, we systematically characterized all seven Arf proteins and found that they have shared and specific functions in governing the growth, development, and pathogenicity of the blast fungus. We have also identified the pathogenicity-related protein MoGga1 as the common adaptor of MoArf1 and MoArl1. Our findings are important because they provide the first comprehensive characterization of the Arf GTPase family proteins and their adaptor protein MoGga1 functioning in a plant-pathogenic fungus, which could help to reveal new fungicide targets to control this devastating disease.

Tunable In Situ Stress and Spontaneous Microwrinkling of Multiscale Heterostructures

Utilizing and tuning internal stress is a powerful strategy to engineer structures and properties of two-dimensional materials and their assemblies. Stress change is commonly induced by either external stress from the substrate, physical changes, or intrinsic surface stress but control of it is limited by interfacial reconstructions, complex processing, or small material scale. Here, we developed an in situ stress method by simultaneously exploiting reaction-induced stress in 2D-based multiscale materials. Molecular-scale intercalating reactions form nanocrystals on the host sheets and make internal stress tunable. Reduced graphene oxide (rGO)–graphitic carbon nitride was obtained with self-organized microwrinkles, using newly formed g-C3N4 as interlayers and thermochemical stress as the driving force. The heterostructures obtained range from macronetwork to few-layer and different 2D materials including MoO3, and BN sheets are proven applicable to this stress-morphing method. This work suggests that in s...

Interfacial Viscoelasticity of Self-Assembled Hydrophobic/Hydrophilic Particles at an Air/Water Interface.

Hydrophobic/hydrophilic mixtures of latex particles at an air/water interface self-assemble, creating space filling, interconnected aggregates as the relative surface fractions of the dissimilar particles approach 0.5, which is reflected both in qualitative observation and fractal dimension of the microstructure. It is hypothesized that this change in microstructure occurs due to an asymmetry in the electrostatic interaction between similar and dissimilar particles caused by polarization of hydrophilic particles by hydrophobic particles. The changes in both microstructure and interparticle interactions significantly impact the interfacial viscoelasticity. As greater shape complexity is observed, interfacial complex moduli can increase by as much as 3 orders of magnitude and interfaces become more elastic.

Water-in-Oil Pickering Emulsions Stabilized by Synergistic Particle–Particle Interactions

Here, we report a novel "double Pickering stabilization" of water-in-oil (W/O) emulsions, where complex formation at the interface between Pickering polyphenol particles adsorbing from the oil side and whey protein microgel (WPM) particles coadsorbing from the aqueous side of the interface is investigated. The interfacial complex formation was strongly dependent on the concentration of WPM particles. At low WPM concentrations, both polyphenol crystals and WPM particles are present at the interface and the water droplets were stabilized through their synergistic action, while at higher concentrations, the WPM particles acted as "colloidal glue" between the water droplets and polyphenol crystals, enhancing the water droplet stability for more than 90 days and prevented coalescence. Via this mechanism, the addition of WPM up to 1 wt % gave a significant improvement in the stability of the W/O emulsions, allowing an increase to a 20 wt % water droplet fraction. The evidence suggests that the complex was probably formed due to electrostatic attraction between oppositely charged polyphenol Pickering particles on the oil side of the interface and WPM Pickering particles mainly on the aqueous side of the interface. Interfacial shear viscosity measurements and monolayer (Langmuir trough) experiments at the air-water interface provided further evidence of this strengthening of the film due to the synergistic particle-particle complex formation at the interface.

Deciphering the heat and mass transfer behaviors of staggered tube bundles in a closed wet cooling tower using a 3-D VOF model

This article presents a three-dimensional CFD model to describe the counter-current air-water flow across the staggered tube bundles in a bench-scale closed wet cooling tower by combining VOF multiphase method and SST k-ω turbulence model. The proposed model can investigate the interfacial heat-mass transfer and complex interaction mechanisms among multiple tubes. Through adding the shear force term and water evaporation in the model, the circumferential distribution of the falling film and air humidity fields are obtained, and the effects of the spray density and the air velocity on the falling film flow mode, air humidity, and transfer process are studied. The results show that, the thinnest water film and maximum evaporation rate are obtained when the circumferential angle is 75° and the spray density is 0.048 kg m−1 s−1, respectively; the air Reynolds number has a greater influence on multiphase heat and mass transfers than that of the spray water Reynolds number.

Water-in-oil Pickering emulsions stabilized by an interfacial complex of water-insoluble polyphenol crystals and protein

Long term stabilization of water-in-oil (W/O) emulsions remains a particularly challenging problem in colloid science. Recent studies have shown that polyphenols act as Pickering stabilizers at the water-oil interface. In this work we propose a novel way to stabilize water droplets via interfacial complex formation. It was observed that polyphenol crystals (curcumin or quercetin) absorb at the interface and provide stabilization of water droplets for several days; however formation of a polyphenol- whey protein (WPI) complex at the water-oil interface revealed a pronounced improvement in the stabilization. The mechanism of complex formation was tested by subjecting the systems to different environmental conditions, such as ionic strength and temperature. The evidence suggests that the complex is probably stabilized by electrostatic attraction between the oppositely-charged polyphenol particles and protein at the interface, although hydrogen bonding between the two components may also contribute. The resulting stable water droplets have a Sauter mean diameter (D3,2) of approximately ∼22 and ∼27 μm for curcumin and quercetin systems, respectively. Emulsions were more stable at pH 3 than at pH 7, due to either weaker complex formation at pH 7 and/or chemical degradation of the polyphenols at this more alkaline pH. Interfacial shear viscosity measurements confirmed that there was strong interfacial complex formation with aqueous WPI concentrations of ∼0.5 wt.%.

Influence of hydrophilic silica nanoparticles on the adsorption layer properties of non-ionic surfactants at water/heptane interface

There is a notable paucity of studies investigating the impact of charged nanoparticles on the interfacial behavior of nonionic surfactants, assuming that the interactions are negligible in the absence of electrostatic forces. Here, we argue about our observations and the existence of a complex interfacial behavior in such systems depending on the type and chemical structure of surfactant. This study set out to investigate the effects of interactions between hydrophilic silica nanoparticles (NP) and non-ionic surfactants on water/heptane dynamic interfacial properties using drop profile analysis tensiometry (PAT). Three surfactants were studied, namely Triton X-100 (significantly soluble in water phase), C12DMPO (well soluble in both phases) and SPAN 80 (oil-soluble). The different chemical structures and partition coefficients of the surfactants enabled us to cover possible interactions and differentiate between bulk and interfacial interactions. We observed that hydrophilic silica NPs had a negligible effect on the interfacial behavior of Triton X-100, that they increased the surface activity of C12DMPO when both compounds are initially in the aqueous phase. Most interestingly is that the added NPs generated unstable interfacial NP-surfactant complexes and reduced the pseudo-equilibrium interfacial tension of oil-soluble surfactant, Span 80, even though NPs and surfactants were in different bulk phases.

Templating Interfacial Nanoparticle Assemblies via in Situ Techniques.

In situ surface modification of nanoparticles has a rich industrial history, but in recent years, it has also received increased attention in the field of directed self-assembly. In situ techniques rely on components within a Pickering emulsion system, such as amphiphiles that act as hydrophobizers or ionic species that screen charges, to drive the interfacial assembly of particles. Instead of stepwise procedures to chemically tune the particle wettability, in situ methods use elements already present within the system to alter the nanoparticle interfacial behavior, often depending on Coulombic interactions to simplify operations. The surface modifications are not contingent on specific chemical reactions, which further enables a multitude of possible nanoparticles to be used within a given system. In recent studies, in situ methods have been combined with external means of shaping the interface to produce materials with high interfacial areas and complex geometries. These systems have facilely tunable properties, enabling their use in an extensive array of applications. In this feature article, in honor of the late Prof. Helmuth Möhwald, we review how in situ techniques have influenced the development of soft, advanced materials, covering the fundamental interfacial phenomena with an outlook on materials science.

Titanium-Dioxide-Based Visible-Light-Sensitive Photocatalysis: Mechanistic Insight and Applications

Titanium dioxide (TiO2) is one of the most practical and prevalent photo-functional materials. Many researchers have endeavored to design several types of visible-light-responsive photocatalysts. In particular, TiO2-based photocatalysts operating under visible light should be urgently designed and developed, in order to take advantage of the unlimited solar light available. Herein, we review recent advances of TiO2-based visible-light-sensitive photocatalysts, classified by the origins of charge separation photo-induced in (1) bulk impurity (N-doping), (2) hetero-junction of metal (Au NPs), and (3) interfacial surface complexes (ISC) and their related photocatalysts. These photocatalysts have demonstrated useful applications, such as photocatalytic mineralization of toxic agents in the polluted atmosphere and water, photocatalytic organic synthesis, and artificial photosynthesis. We wish to provide comprehension and enlightenment of modification strategies and mechanistic insight, and to inspire future work.

Efficiency of the interfacial charge transfer complex between TiO2 nanoparticles and caffeic acid against DNA damage in vitro: A combinatorial analysis

The genotoxic and antigenotoxic behavior of the interfacial charge transfer (ICT) complex between nano-sized TiO2 particles and caffeic acid (CA) was studied in in vitro experiments. The formation of the ICT complex is indicated by the appearance of absorption in visible-spectral range. The continual variations method indicated bridging coordination between the ligand, caffeic acid, and the surface Ti atoms, while the stability constant of the ICT complex was found to be 1.5?103 mol-1 L. An agreement between the experimental data and the theoretical results, based on the density functional theory, was found. The ICT complex and its components did not display genotoxicity in the broad concentration range 0.4?8.0 mg mL-1 TiO2 at a mole ratio c(TiO2)/c(CA) = 8. On the other hand, post-treatment of damaged DNA by the ICT complex induced antigenotoxic effect at lower concentrations, but at higher concentrations, 5.125?10.250 mg mL-1 ICT, the ICT complex did not show any beneficial effect on H2O2-induced DNA damaged cells. The experimental data were analyzed using the combinatorial method to determine the effect of component interaction on the genotoxic and antigenotoxic behavior of the ICT complex.

TOR-autophagy branch signaling via Imp1 dictates plant-microbe biotrophic interface longevity.

Like other intracellular eukaryotic phytopathogens, the devastating rice blast fungus Magnaporthe (Pyricularia) oryzae first infects living host cells by elaborating invasive hyphae (IH) surrounded by a plant-derived membrane. This forms an extended biotrophic interface enclosing an apoplastic compartment into which fungal effectors can be deployed to evade host detection. M. oryzae also forms a focal, plant membrane-rich structure, the biotrophic interfacial complex (BIC), that accumulates cytoplasmic effectors for translocation into host cells. Molecular decision-making processes integrating fungal growth and metabolism in host cells with interface function and dynamics are unknown. Here, we report unanticipated roles for the M. oryzae Target-of-Rapamycin (TOR) nutrient-signaling pathway in mediating plant-fungal biotrophic interface membrane integrity. Through a forward genetics screen for M. oryzae mutant strains resistant to the specific TOR kinase inhibitor rapamycin, we discovered IMP1 encoding a novel vacuolar protein required for membrane trafficking, V-ATPase assembly, organelle acidification and autophagy induction. During infection, Δimp1 deletants developed intracellular IH in the first infected rice cell following cuticle penetration. However, fluorescently labeled effector probes revealed that interface membrane integrity became compromised as biotrophy progressed, abolishing the BIC and releasing apoplastic effectors into host cytoplasm. Growth between rice cells was restricted. TOR-independent autophagy activation in Δimp1 deletants (following infection) remediated interface function and cell-to-cell growth. Autophagy inhibition in wild type (following infection) recapitulated Δimp1. In addition to vacuoles, Imp1GFP localized to IH membranes in an autophagy-dependent manner. Collectively, our results suggest TOR-Imp1-autophagy branch signaling mediates membrane homeostasis to prevent catastrophic erosion of the biotrophic interface, thus facilitating fungal growth in living rice cells. The significance of this work lays in elaborating a novel molecular mechanism of infection stressing the dominance of fungal metabolism and metabolic control in sustaining long-term plant-microbe interactions. This work also has implications for understanding the enigmatic biotrophy to necrotrophy transition.

Accumulation of phosphoinositides in distinct regions of the periarbuscular membrane.

Phosphoinositides and phosphatidic acid are small anionic lipids that comprise a minor proportion of total membrane lipids in eukaryotic cells but influence a broad range of cellular processes including endomembrane trafficking, signaling, exocytosis and endocytosis. To investigate the spatial distribution of phosphoinositides during arbuscular mycorrhizal symbiosis, we generated fluorescent reporters of PI(4,5)P2 and PI4P, as well as phosphatidic acid and diacylglycerol and used them to monitor lipid distribution on the cytoplasmic side of membrane bilayers in colonized cortical cells. The PI4P reporter accumulated strongly on the periarbuscular membrane (PAM) and transiently labeled Golgi bodies, while the PA reporter showed differential labeling of endomembranes and the PAM. Surprisingly, the PI(4,5)P2 reporter accumulated in small, discrete regions of the PAM on the arbuscule trunks, frequently in two regions on opposing sides of the hypha. A mutant reporter with reduced PI(4,5)P2 binding capacity did not show these accumulations. The PI(4,5)P2 -rich regions were detected at all phases of arbuscule development following branching, co-localized with membrane marker proteins potentially indicating high membrane bilayer content, and were associated with an alteration in morphology of the hypha. A possible analogy to the biotrophic interfacial membrane complex formed in rice infected with Magnaporthe orzyae is discussed.

State memory in solution gated epitaxial graphene

We studied electrical transport in transistors fabricated on a surface of high quality epitaxial graphene with density of defects as low as 5·1010 cm−2 and observed quasistatic hysteresis with a time constant in a scale of hours. This constant is in a few orders of magnitude greater than the constant previously reported in CVD graphene. The hysteresis observed here can be described as a shift of ∼+2V of the Dirac point measured during a gate voltage increase from the position of the Dirac point measured during a gate voltage decrease. This hysteresis can be characterized as a nonvolatile quasistatic state memory effect in which the state of the gated graphene is determined by its initial state prior to entering the hysteretic region. Due to this effect the difference in resistance of the gated graphene measured in the hysteretic region at the same applied voltages can be as high as 70%. The observed effect can be explained by assuming that charge carriers in graphene and oppositely charged molecular ions from the solution form quasistable interfacial complexes at the graphene interface. These complexes likely preserve the initial state by preventing charge carriers in graphene from discharging in the hysteretic region.

Solubilization behaviors of interfacial lutetium-extractant complex in a solvent extraction system

Knowledge of the solubilization behaviors of rare-earth-extractant complex is mandatory for full comprehension of interfacial phenomenon and intermediate state of rare earth (RE) ion transport from water to oil during solvent extraction. The lutetium with 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (P507) extraction system was explored as a case study for the solubilization behaviors in this paper. With a quantitative analysis of a white crud obtained in the practical process, the results demonstrate that the insoluble REL3 (L = the anion of P507) complex enriches at the oil/water interface and forms the network polymers. Besides, with the increase of RE loading ratios in the oil phase, the interfacial tension increases while the free ligand in the bulk phase decreases, which results in the flocculation of REL3 complex and the formation of polymers at the interface. Furthermore, the properties of the oil phase and the interface reveal that the free ligand can solubilize the REL3 complex along with the transfer of water from microemulsion to aqueous phase. In addition, the change of aqueous acidity can regulate the solubilization behaviors of the interfacial complex to improve RE extraction efficiency. These fundamental studies will hopefully provide new insights into the solubilization of metal-extractant complex and a technical guidance to the transfer of RE from water to oil.

The structure of a lanthanide complex at an extractant/water interface studied using heterodyne-detected vibrational sum frequency generation.

Solvent extraction plays an integral part in the separation and purification of metals. Because extractants generally used as complexing agents for metal extractions, such as di-(2-ethylhexyl)phosphoric acid (HDEHP) for lanthanide extractions, are amphiphilic, they come to an organic/water interface, and the interface plays a crucial role as the site of the formation of metal complexes and the subsequent transfer reaction to an organic phase. Despite the importance of the interface for metal solvent extractions, its molecular-level structure is unclear because of the experimental difficulties. Here we studied the structure of a trivalent europium (Eu3+) complex with HDEHP formed at the HDEHP monolayer/water interface using heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. The study on the HDEHP/water interface enables us to investigate the structure of the interfacial Eu3+ complex by excluding the migration of Eu3+ into an organic phase after the complex formation at the interface. The interface-selective vibrational Imχ(2) spectra observed using HD-VSFG of the interface of HDEHP/aqueous Eu(NO3)3 solution in the 2800-3500 cm-1 region indicate that Eu3+ at the HDEHP/water interface is bonded by HDEHP from the air side and by water molecules from the water side. To the best of our knowledge, such metal complex structures have not been identified in organic or water solutions.

Two-Step Adsorption of PtCl62– Complexes at a Charged Langmuir Monolayer: Role of Hydration and Ion Correlations

Anion exchange at positively charged interfaces plays an important role in a variety of physical and chemical processes. However, the molecular scale details of these processes, especially with heavy and large anionic complexes, are not well-understood. We studied the adsorption of $PtCl_6^{2-}$ anionic complexes to floating DPTAP monolayers in the presence of excess $Cl^-$ as a function of the bulk chlorometalate concentration. In situ x-ray scattering and fluorescence measurements, which are element and depth sensitive, show that the chlorometalate ions only adsorb in the diffuse layer at lower concentrations, while they adsorb predominantly in the Stern layer at higher concentrations. The response of DPTAP molecules to the adsorbed ions is determined independently by grazing incidence x-ray diffraction, and supports this picture. Molecular dynamics simulations further elucidate the nanoscale structure of the interfacial complexes. The results suggest that ion hydration and ion-ion correlations play a key role in the competitive adsorption process.

Environmental Effects on Zirconium Hydroxide Nanoparticles and Chemical Warfare Agent Decomposition: Implications of Atmospheric Water and Carbon Dioxide.

Zirconium hydroxide (Zr(OH)4) has excellent sorption properties and wide-ranging reactivity toward numerous types of chemical warfare agents (CWAs) and toxic industrial chemicals. Under pristine laboratory conditions, the effectiveness of Zr(OH)4 has been attributed to a combination of diverse surface hydroxyl species and defects; however, atmospheric components (e.g., CO2, H2O, etc.) and trace contaminants can form adsorbates with potentially detrimental impact to the chemical reactivity of Zr(OH)4. Here, we report the hydrolysis of a CWA simulant, dimethyl methylphosphonate (DMMP) on Zr(OH)4 determined by gas chromatography-mass spectrometry and in situ attenuated total reflectance Fourier transform infrared spectroscopy under ambient conditions. DMMP dosing on Zr(OH)4 formed methyl methylphosphonate and methoxy degradation products on free bridging and terminal hydroxyl sites of Zr(OH)4 under all evaluated environmental conditions. CO2 dosing on Zr(OH)4 formed adsorbed (bi)carbonates and interfacial carbonate complexes with relative stability dependent on CO2 and H2O partial pressures. High concentrations of CO2 reduced DMMP decomposition kinetics by occupying Zr(OH)4 active sites with carbonaceous adsorbates. Elevated humidity promoted hydrolysis of adsorbed DMMP on Zr(OH)4 to produce methanol and regenerated free hydroxyl species. Hydrolysis of DMMP by Zr(OH)4 occurred under all conditions evaluated, demonstrating promise for chemical decontamination under diverse, real-world conditions.

Quantification of Membrane Protein-Detergent Complex Interactions.

Although fundamentally significant in structural, chemical, and membrane biology, the interfacial protein-detergent complex (PDC) interactions have been modestly examined because of the complicated behavior of both detergents and membrane proteins in aqueous phase. Membrane proteins are prone to unproductive aggregation resulting from poor detergent solvation, but the participating forces in this phenomenon remain ambiguous. Here, we show that using rational membrane protein design, targeted chemical modification, and steady-state fluorescence polarization spectroscopy, the detergent desolvation of membrane proteins can be quantitatively evaluated. We demonstrate that depleting the detergent in the sample well produced a two-state transition of membrane proteins between a fully detergent-solvated state and a detergent-desolvated state, the nature of which depended on the interfacial PDC interactions. Using a panel of six membrane proteins of varying hydrophobic topography, structural fingerprint, and charge distribution on the solvent-accessible surface, we provide direct experimental evidence for the contributions of the electrostatic and hydrophobic interactions to the protein solvation properties. Moreover, all-atom molecular dynamics simulations report the major contribution of the hydrophobic forces exerted at the PDC interface. This semiquantitative approach might be extended in the future to include studies of the interfacial PDC interactions of other challenging membrane protein systems of unknown structure. This would have practical importance in protein extraction, solubilization, stabilization, and crystallization.

DFT study of benzyl alcohol/TiO2 interfacial surface complex: reaction pathway and mechanism of visible light absorption.

We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H2O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO2 surface. Graphical Abstract The chemisorption of benzyl alcohol on TiO2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light.