Light-induced Charge Transfer Research Articles

Multifunctional Polyoxometalate Platforms for Supramolecular Light-Driven Hydrogen Evolution*.

Multifunctional supramolecular systems are a central research topic in light‐driven solar energy conversion. Here, we report a polyoxometalate (POM)‐based supramolecular dyad, where two platinum‐complex hydrogen evolution catalysts are covalently anchored to an Anderson polyoxomolybdate anion. Supramolecular electrostatic coupling of the system to an iridium photosensitizer enables visible light‐driven hydrogen evolution. Combined theory and experiment demonstrate the multifunctionality of the POM, which acts as photosensitizer/catalyst‐binding‐site[1] and facilitates light‐induced charge‐transfer and catalytic turnover. Chemical modification of the Pt‐catalyst site leads to increased hydrogen evolution reactivity. Mechanistic studies shed light on the role of the individual components and provide a molecular understanding of the interactions which govern stability and reactivity. The system could serve as a blueprint for multifunctional polyoxometalates in energy conversion and storage.

Defective Black TiO2: Effects of Annealing Atmospheres and Urea Addition on the Properties and Photocatalytic Activities.

A series of black TiO2 with and without the addition of urea were successfully prepared using a simple one-step synthetic method by calcination under different atmospheres (vacuum, He, or N2). The physicochemical, optical, and light-induced charge transfer properties of the as-prepared samples were characterized by various techniques. It was found that a vacuum atmosphere was more beneficial for the formation of oxygen vacancies (OVs) than the inert gases (He and N2) and the addition of urea-inhibited OVs formation. The samples annealed in the vacuum condition exhibited better visible-light adsorption abilities, narrower bandgaps, higher photo-induced charge separation efficiency, and lower recombination rates. Hydroxyl radicals (·OH) were the dominant oxidative species in the samples annealed under a vacuum. Finally, the samples annealed under vacuum conditions displayed higher photocatalytic activity for methylene blue (MB) degradation than the samples annealed under He or N2. Based on the above, this study provides new insights into the effects of annealing atmospheres and urea addition on the properties of black TiO2.

Electric Field-Modulated Charge Transfer in Geometrically Tailored MoX2/WX2 (X = S, Se) Heterostructures

Light-induced interlayer charge transfer in staggered-type heterostructures (HSs) in transition-metal dichalcogenides provides the opportunity to improve the performance of optoelectronic applications. Herein, we employ density functional theory to investigate the vertical electric-field-controlled interlayer charge transfer in stacked MoX2/WX2 (X=S, Se) HSs. Upon application of electric field from −3 to 3 V/nm, we observe the band-alignment transition, band inversion, and offset variations in these HSs. Furthermore, these electric fields are found to modulate charge localization/delocalization across the layers, which provides insight into charge transfer. The positive electric field is supposed to localize the charges in WS2, whereas the charges are localized in MoS2 at negative electric field. Based on charge localization/delocalization, our study suggests that the interlayer hole transfer upon MoS2 photoexcitation can be suppressed at higher positive electric fields, whereas electron transfer can be blocked by excitation of WS2. In contrast, negative electric fields (of −3 V/nm) can induce interlayer hole and electron transfer. Owing to the tunability of interlayer charge transfer by means of a vertical electric field, our findings bear paramount importance in modulating electron–hole recombination and charge-transfer time, which is beneficial for future optoelectronic devices.

Light-Induced Charge Transfer in Two-Dimensional Hybrid Lead Halide Perovskites

Light-Induced Charge Transfer in Two-Dimensional Hybrid Lead Halide Perovskites

Light-Induced Charge Transfer from Transition-Metal-Doped Aluminum Clusters to Carbon Dioxide.

Charge transfer between molecules and catalysts plays a critical role in determining the efficiency and yield of photochemical catalytic processes. In this paper, we study light-induced electron transfer between transition-metal-doped aluminum clusters and CO2 molecules using first-principles time-dependent density-functional theory. Specifically, we carry out calculations for a range of dopants (Zr, Mn, Fe, Ru, Co, Ni, and Cu) and find that the resulting systems fall into two categories: Cu- and Fe-doped clusters exhibit no ground-state charge transfer, weak CO2 adsorption, and light-induced electron transfer into the CO2. In all other systems, we observe ground-state electron transfer into the CO2 resulting in strong adsorption and predominantly light-induced electron back-transfer from the CO2 into the cluster. These findings pave the way toward a rational design of atomically precise aluminum photocatalysts.

Ultrafast Electron Transfer from CdSe Quantum Dots to an [FeFe]-Hydrogenase Mimic.

The combination of CdSe nanoparticles as photosensitizers with [FeFe]-hydrogenase mimics is known to result in efficient systems for light-driven hydrogen generation with reported turnover numbers in the order of 104-106. Nevertheless, little is known about the details of the light-induced charge-transfer processes. Here, we investigate the time scale of light-induced electron transfer kinetics for a simple model system consisting of CdSe quantum dots (QDs) of 2.0 nm diameter and a simple [FeFe]-hydrogenase mimic adsorbed to the QD surface under noncatalytic conditions. Our (time-resolved) spectroscopic investigation shows that both hot electron transfer on a sub-ps time scale and band-edge electron transfer on a sub-10 ps time scale from photoexcited QDs to adsorbed [FeFe]-hydrogenase mimics occur. Fast recombination via back electron transfer is observed in the absence of a sacrificial agent or protons which, under real catalytic conditions, would quench remaining holes or could stabilize the charge separation, respectively.

Photocathodes beyond NiO: charge transfer dynamics in a \u03c0-conjugated polymer functionalized with Ru photosensitizers

A conductive polymer (poly(p-phenylenevinylene), PPV) was covalently modified with RuII complexes to develop an all-polymer photocathode as a conceptual alternative to dye-sensitized NiO, which is the current state-of-the-art photocathode in solar fuels research. Photocathodes require efficient light-induced charge-transfer processes and we investigated these processes within our photocathodes using spectroscopic and spectro-electrochemical techniques. Ultrafast hole-injection dynamics in the polymer were investigated by transient absorption spectroscopy and charge transfer at the electrode–electrolyte interface was examined with chopped-light chronoamperometry. Light-induced hole injection from the photosensitizers into the PPV backbone was observed within 10 ps and the resulting charge-separated state (CSS) recombined within ~ 5 ns. This is comparable to CSS lifetimes of conventional NiO-photocathodes. Chopped-light chronoamperometry indicates enhanced charge-transfer at the electrode–electrolyte interface upon sensitization of the PPV with the RuII complexes and p-type behavior of the photocathode. The results presented here show that the polymer backbone behaves like classical molecularly sensitized NiO photocathodes and operates as a hole accepting semiconductor. This in turn demonstrates the feasibility of all-polymer photocathodes for application in solar energy conversion.

Interfacing Carbon Dots for Charge-Transfer Processes.

Carbon dots (CDs) are a booming material and the most recent incomer in the big family of carbon nanostructures. Specifically, CDs are nanosized fluorescent core-shell nanoparticles with tunable absorption and emission spectra, with high solubility in aqueous media and common organic solvents. Herein, the origins and the development of these unique nanoscale structures are discussed, key synthetic routes are briefly described, and the utilization of CDs in light-induced charge-transfer schemes is mainly focused upon. Beyond the impact of the CD's surface on the photoluminescence properties, functionalization, by covalent or supramolecular means, permits controllable incorporation of new functionalities with novel photophysical properties. Furthermore, the dual nature of CDs as electron donating or electron accepting species, unveiled upon interfacing them with organic chromophores, highlights their potentiality in managing diverse charge-transfer processes. Novel mechanisms, such as symmetry-breaking photoinduced charge-transfer can be activated upon covalent functionalization of CDs with organic dyes. Without a doubt, participation of CDs in energy conversion schemes opens up a wide avenue that may lead to the development of novel prototype devices suitable for technological applications and related to photonics and optoelectronics.

Counterion Migration Driven by Light-Induced Intramolecular Charge Transfer.

A series of D−π–A+ pyridinium compounds, in which D = −NPh2 and A+ = −PyMe+ are linked by various amounts of linear phenyl spacers, were strategically designed and synthesized. Their characterization revealed the presence of excited-state intramolecular charge transfer (ESICT) that triggers a corresponding response from the counterion. In medium and strong polar solvents, the fast solvent relaxation occurring after ESICT overwhelms the counterion effect, showing typical emission solvatochromism. In weakly polar solvents, ESICT induces counteranion migration for electrostatic stabilization, the time scale of which is dependent on the radius of the counteranion, the length of the π-linker, and the viscosity of the solvent. In low-viscosity organic solvents such as toluene, counteranion migration occurs within several tens to hundreds of picoseconds, resulting in a time-dependent continuous emission that can be resolved from the spectral temporal evolution. Concrete evidence for this is provided by the chemical synthesis of a D−π–A+ pyridinium–sulfur trioxide– zwitterion, where anion migration is restricted due to its internally locked ion pair. As a result, only a single emission band can be observed. These comprehensive studies prove that the ion migration process may be significant for a wide range of ESICT-type ionic fluorophores. Such an ionic movement, triggered by optically pumped ESICT of the D−π–A+ dyad, is similar to the molecular machine driven by the redox reaction, but with a facile access and fast response.

The dynamics of light-induced interfacial charge transfer of different dyes in dye-sensitized solar cells studied by ab initio molecular dynamics.

The charge-transport dynamics at the dye-TiO2 interface plays a vital role for the resulting power conversion efficiency (PCE) of dye sensitized solar cells (DSSCs). In this work, we have investigated the charge-exchange dynamics for a series of organic dyes, of different complexity, and a small model of the semiconductor substrate TiO2. The dyes studied involve L1, D35 and LEG4, all well-known organic dyes commonly used in DSSCs. The computational studies have been based on ab initio molecular dynamics (aiMD) simulations, from which structural snapshots have been collected. Estimates of the charge-transfer rate constants of the central exchange processes in the systems have been computed. All dyes show similar properties, and differences are mainly of quantitative character. The processes studied were the electron injection from the photoexcited dye, the hole transfer from TiO2 to the dye and the recombination loss from TiO2 to the dye. It is notable that the electronic coupling/transfer rates differ significantly between the snapshot configurations harvested from the aiMD simulations. The differences are significant and indicate that a single geometrically optimized conformation normally obtained from static quantum-chemistry calculations may provide arbitrary results. Both protonated and deprotonated dye systems were studied. The differences mainly appear in the rate constant of recombination loss between the protonated and the deprotonated dyes, where recombination losses take place at significantly higher rates. The inclusion of lithium ions close to the deprotonated dye carboxylate anchoring group mitigates recombination in a similar way as when protons are retained at the carboxylate group. This may give insight into the performance-enchancing effects of added salts of polarizing cations to the DSSC electrolyte. In addition, solvent effects can retard charge recombination by about two orders of magnitude, which demonstrates that the presence of a solvent will increase the lifetime of injected electrons and thus contribute to a higher PCE of DSSCs. It is also notable that no simple correlation can be identified between high/low transfer rate constants and specific structural arrangements in terms of atom-atom distances, angles or dihedral arrangements of dye sub-units.

Photo-enhanced Seebeck effect of a highly conductive thermoelectric material

The Seebeck coefficient of the composites of PEDOT:PSS and TiO2nanoparticles can be greatly enhanced by exposure to UV light. This is attributed to the light-induced charge transfer from TiO2to PEDOT:PSS.

Probing the dye-semiconductor interface in dye-sensitized NiO solar cells.

The development of p-type dye-sensitized solar cells (p-DSSCs) offers an opportunity to assemble tandem photoelectrochemical solar cells with higher efficiencies than TiO2-based photoanodes, pioneered by O'Regan and Grätzel [Nature 353, 737-740 (1991)]. This paper describes an investigation into the behavior at the interfaces in p-DSSCs, using a series of BODIPY dyes, BOD1-3. The three dyes have different structural and electronic properties, which lead to different performances in p-DSSCs. We have applied photoelectron spectroscopy and transient absorption spectroscopy to rationalize these differences. The results show that the electronic orbitals of the dyes are appropriately aligned with the valence band of the NiO semiconductor to promote light-induced charge transfer, but charge-recombination is too fast for efficient dye regeneration by the electrolyte. We attribute this fast recombination, which limits the efficiency of the solar cells, to the electronic structure of the dye and the presence of Ni3+ recombination sites at the NiO surface.

Regulatory Impact of the C-Terminal Tail on Charge Transfer Pathways in Drosophila Cryptochrome.

Interconnected transcriptional and translational feedback loops are at the core of the molecular mechanism of the circadian clock. Such feedback loops are synchronized to external light entrainment by the blue light photoreceptor cryptochrome (CRY) that undergoes conformational changes upon light absorption by an unknown photoexcitation mechanism. Light-induced charge transfer (CT) reactions in Drosophila CRY (dCRY) are investigated by state-of-the-art simulations that reveal a complex, multi-redox site nature of CT dynamics on the microscopic level. The simulations consider redox-active chromophores of the tryptophan triad (Trp triad) and further account for pathways mediated by W314 and W422 residues proximate to the C-terminal tail (CTT), thus avoiding a pre-bias to specific W-mediated CT pathways. The conducted dissipative quantum dynamics simulations employ microscopically derived model Hamiltonians and display complex and ultrafast CT dynamics on the picosecond timescale, subtly balanced by the electrostatic environment of dCRY. In silicio point mutations provide a microscopic basis for rationalizing particular CT directionality and demonstrate the degree of electrostatic control realized by a discrete set of charged amino acid residues. The predicted participation of CT states in proximity to the CTT relates the directionality of CT reactions to the spatial vicinity of a linear interaction motif. The results stress the importance of CTT directional charge transfer in addition to charge transfer via the Trp triad and call for the use of full-length CRY models including the interactions of photolyase homology region (PHR) and CTT domains.

Visible Light Electromagnetic Interaction of PM567 Chiral Dye for Asymmetric Photocatalysis, a First-Principles Investigation

In asymmetric photocatalytic reactions, it is necessary to study the mechanism of the asymmetric electromagnetic interaction between molecules and light. In this work, we theoretically studied the electromagnetic interactions between the light-induced charge transfer reaction and the chiral reaction of PM567 dye. We found that the chiral responses of molecules in different wavelength ranges were partially due to pyrromethene and binaphthalene. Therefore, the catalytic sites with different chirality also corresponds to the two-part groups. Through quantitative analysis, we found the entire analysis process to be complete and self-consistent.

Plasmon-enabled degradation of organic micropollutants in water by visible-light illumination of Janus gold nanorods

The development of sustainable methods for the degradation of pollutants in water is an ongoing critical challenge. Anthropogenic organic micropollutants such as pharmaceuticals, present in our water supplies in trace quantities, are currently not remediated by conventional treatment processes. Here, we report an initial demonstration of the oxidative degradation of organic micropollutants using specially designed nanoparticles and visible-wavelength sunlight. Gold "Janus" nanorods (Au JNRs), partially coated with silica to enhance their colloidal stability in aqueous solutions while also maintaining a partially uncoated Au surface to facilitate photocatalysis, were synthesized. Au JNRs were dispersed in an aqueous solution containing peroxydisulfate (PDS), where oxidative degradation of both simulant and actual organic micropollutants was observed. Photothermal heating, light-induced hot electron-driven charge transfer, and direct electron shuttling under dark conditions all contribute to the observed oxidation chemistry. This work not only provides an ideal platform for studying plasmonic photochemistry in aqueous medium but also opens the door for nanoengineered, solar-based methods to remediate recalcitrant micropollutants in water supplies.

Light-induced charge transfer at the CH3NH3PbI3/TiO2 interface—a low-temperature photo-electron paramagnetic resonance assay

The performance of organic–inorganic metal halide perovskites-based (MHPs) photovoltaic devices critically depends on the design and material properties of the interface between the light-harvesting MHP layer and the electron transport layer (ETL). Therefore, the detailed insight into the transfer mechanisms of photogenerated carriers at the ETL/MHP interface is of utmost importance. Owing to its high charge mobilities and well-matched band structure with MHPs, titanium dioxide (TiO2) has emerged as the most widely used ETL material in MHPs-based photovoltaic devices. Here, we report a contactless method to directly track the photo-carriers at the ETL/MHP interface using the technique of low-temperature electron paramagnetic resonance (EPR) in combination with in situ illuminations (Photo-EPR). Specifically, we focus on a model nanohybrid material consisting of TiO2-based nanowires (TiO2NWs) dispersed in the polycrystalline methylammonium lead triiodide (MAPbI3) matrix. Our approach is based on observation of the light-induced decrease in intensity of the EPR signal of paramagnetic Ti3+ () in non-stoichiometric TiO2NWs. We associate the diminishment of the EPR signal with the photo-excited electrons that cross the ETL/MHP interface and contribute to the conversion of Ti3+ states to EPR-silent Ti2+ states. Overall, we infer that the technique of low-temperature Photo-EPR is an effective strategy to study the transfer mechanisms of photogenerated carriers at the ETL/MHP interface in MAPbI3-based photovoltaic and photoelectronic systems.

Silver Nanocubes Coated in Ceria: Core/Shell Size Effects on Light-Induced Charge Transfer.

Plasmonic sensitization of semiconductors is an attractive approach to increase light-induced photocatalytic performance; one method is to use plasmonic nanostructures in core@shell geometry. The occurrence and mechanism of synergetic effects in photocatalysis of such geometries are under intense debate and proposed to occur either through light-induced charge transfer (CT) or through thermal effects. This study focuses on the relation between the dimensions of Ag@CeO2 nanocubes, the wavelength-dependent efficiency, and the mechanism of light-induced direct CT. A 4-mercaptobenzoic acid (4-MBA) linker between core and shell acts as a Raman probe for CT. For all Ag@CeO2 nanocubes, CT increases with decreasing excitation wavelength, with notable increase at and below 514 nm. This is fully explainable by CT from silver to the 4-MBA LUMO, with the increase for excitation wavelengths that exceed the Ag/4-MBA LUMO gap of 2.28 eV (543 nm). A second general trend observed is an increase in CT yield with ceria shell thickness, which is assigned to relaxation of the excited electron further into the ceria conduction band, potentially producing defects.

The visible-light-driven photo-reduction of Cr(VI) by formic acid in aqueous solution

To study the applicability and mechanism of the visible-light-driven photo-reduction of Cr(VI) is important since it will elucidate the chromium cycle in natural circumstances, and since this reduction reaction is important in treating wastewater contaminated by Cr(VI). Herein, we conducted an in-depth mechanism study for this process using formic acid as electron donor. The positive dependence of the Cr(VI) conversion on the incident light intensity and the good match between the apparent quantum yield (0.0039–0.39%) and the light absorption spectrum (550–365 nm) suggests a light-induced mechanism. The light-induced charge transfer occurs through the ligand-to-metal charge transfer state of the complex which forms between one dichromate molecule and two formic acid molecules through symmetrical or asymmetrical configuration as demonstrated by DFT simulation. EPR analysis further proves that this reaction occurs through a stepwise process with Cr(V) and Cr(IV) as the intermediates. The practical use of this photochemical procedure with broad electron donor scope and wide pH, reaction temperature, and initial Cr(VI) concentration ranges, is proven by the application potential evaluation. The efficient reduction of Cr(VI) by formic acid under sunlight further proves the applicability of this photochemical procedure for the treatment of Cr(VI) contaminated wastewater. Development of the present study into both the treatment of Cr(VI) contaminated wastewater, and other visible-light-driven photo-redox reactions between metals and organics are the subject of further research and results can be expected in the near future.

Ultrafast Intramolecular and Solvation Dynamics in 4,7-Bis (4,5-dibutylbenzo[1,2-b:4,3-b′]bisthiophene[1,2-b:4,3-b′]bisthiophen-2-yl)-2,1,3-benzothiadiazole

We report a combined approach of stationary and time-resolved fluorescence measurements and ultraviolet–visible (UV–vis) transient absorption spectroscopy (TAS) along with ab initio calculations, which provide an overall picture of the dynamics occurring after excitation in a push–pull molecule, namely, 4,7-bis (4,5-dibutylbenzo[1,2-b:4,3-b′]bisthiophene[1,2-b:4,3-b′]bisthiophen-2-yl)-2,1,3-benzothiadiazole. The analysis of the emission spectra in solvents of different polarities reveals the presence of three conformers whose structures differ in the orientation of the 4,5-dibutylbenzo-bisthiophene groups and in their planarity with respect to the benzothiadiazole acceptor group. The Kawski method allows us to estimate the ground- and first-excited state dipole moments (μg and μe) for the three conformers. We find values of μe similar for the three conformers and higher than the relative μg values as can be expected from a push–pull molecule undergoing a light-induced charge-transfer (CT) transition. UV–vis TAS in different solvents highlights the instantaneous (within our instrumental resolution) formation of a locally excited S1 state (accompanied by a big change in the dipole moment with respect to S0), which undergoes a rapid intramolecular CT (ICT) assisted by molecule planarization [planar ICT (PICT)]. The strong dipole–dipole interactions with the polarized solvent molecules stabilize the S1 CT state that decays principally through fluorescence emission. Both PICT and solvation dynamics are responsible for the big Stokes’ shift characterizing the molecule, particularly in polar solvents. The fluorescence lifetimes are substantially longer in polar solvents, and also fluorescence quantum yields are higher in polar solvents. We conclude that the radiative relaxation time increases when molecular planarization of the S1 emissive state takes place, and this condition is favored in polar solvents where local dipole–dipole interactions support the structural stabilization of the CT emissive state. In the poly(methyl methacrylate) matrix, the structural and solvation dynamics are strongly inhibited, leading to reduction of nonradiative processes and to shortening of the fluorescence relaxation time.

Resonance Raman Spectro-Electrochemistry to Illuminate Photo-Induced Molecular Reaction Pathways.

Electron transfer reactions play a key role for artificial solar energy conversion, however, the underlying reaction mechanisms and the interplay with the molecular structure are still poorly understood due to the complexity of the reaction pathways and ultrafast timescales. In order to investigate such light-induced reaction pathways, a new spectroscopic tool has been applied, which combines UV-vis and resonance Raman spectroscopy at multiple excitation wavelengths with electrochemistry in a thin-layer electrochemical cell to study [RuII(tbtpy)2]2+ (tbtpy = tri-tert-butyl-2,2′:6′,2′′-terpyridine) as a model compound for the photo-activated electron donor in structurally related molecular and supramolecular assemblies. The new spectroscopic method substantiates previous suggestions regarding the reduction mechanism of this complex by localizing photo-electrons and identifying structural changes of metastable intermediates along the reaction cascade. This has been realized by monitoring selective enhancement of Raman-active vibrations associated with structural changes upon electronic absorption when tuning the excitation wavelength into new UV-vis absorption bands of intermediate structures. Additional interpretation of shifts in Raman band positions upon reduction with the help of quantum chemical calculations provides a consistent picture of the sequential reduction of the individual terpyridine ligands, i.e., the first reduction results in the monocation [(tbtpy)Ru(tbtpy•)]+, while the second reduction generates [(tbtpy•)Ru(tbtpy•)]0 of triplet multiplicity. Therefore, the combination of this versatile spectro-electrochemical tool allows us to deepen the fundamental understanding of light-induced charge transfer processes in more relevant and complex systems.