EPR investigation of TiO2 nanoparticles with temperature-dependent properties

An in situ electron paramagnetic resonance (EPR) study has been carried out for anatase (Hombikat UV100) and rutile TiO(2) nanoparticles at liquid helium (He) temperature (4.2 K) under UV irradiation. Rutile titania was synthesized by ultrasonic irradiation with titanium tetrachloride (TiCl(4)) as the precursor. XRD and Raman results evidence the crystallinity of titania phases. The nature of trapped electrons and holes has been investigated by EPR spectroscopy under air and vacuum conditions. Illumination of TiO(2) powder (anatase and rutile) at 4.2 K resulted in the detection of electrons being trapped at Ti(4+) sites within the bulk and holes trapped at lattice oxide ions at the surface. The stability of electron traps was very sensitive to temperature in both phases of TiO(2). The annealing kinetics of the EPR detected radicals has been studied from 4.2 K to ambient temperature and also for calcined titania particles from 523 to 1273 K.     

Recombination pathways in the Degussa P25 formulation of TiO2: surface versus lattice mechanisms

Charge migration between electron trapping sites within the mixed-phase titania photocatalyst Degussa P25 has been studied. In addition to previously described lattice electron trapping sites on both anatase and rutile phases, surface electron trapping sites and an anatase-rutile interface trapping site specific to Degussa P25 are identified. The relationship between these sites and recombination with surface hole trapping sites is also determined. It is experimentally shown that upon band-gap illumination holes appear at the surface and preferentially recombine with electrons in surface trapping sites. These findings indicate that in mixed-phase TiO2, such as Degussa P25, photogenerated holes are trapped exclusively on the particle surface, while photogenerated electrons are trapped within the nanoparticle lattice. Recombination reactions are dominated by surface reactions that follow charge migration. These findings indicate that, in mixed-phase TiO(2), such as Degussa P25, a random flight mechanism of recombination predominates. Such knowledge simplifies the mechanistic mathematical models used for process design and points the way for improving future oxidative titania catalysts.     

Low temperature kinetics and energetics of the electron and hole traps in irradiated TiO2 nanoparticles as revealed by EPR spectroscopy

We have monitored exclusively the dynamics of photogenerated charge carriers trapping in deep traps and trapped electron-hole recombination in UV irradiated anatase TiO2 powders by electron paramagnetic resonance (EPR) spectroscopy at 10 K. The results reveal that the strategy of using low temperatures contributes to the stabilization of the charged pair states for hours by reducing the rate of electron-hole recombination processes. Since only the localized states such as holes trapped at oxygen anions and electrons trapped at coordinatively unsaturated cations are accessible to EPR spectroscopy, the time-dependent population and depopulation of these EPR signals reflect the kinetics and energetics of these trap states. The data support a model of sequential accumulation of deep trap site populations in which the initial fast direct trapping into a deep trap site is followed by slower carrier trap-to-trap hopping until a deep trap is encountered for both photogenerated electrons and holes. Effective modeling of the subsequent decay of trapped-holes is achieved by employing a first-order kinetics, whereas the decay of either surface- or inner-trapped electrons has both a fast and a slow component. The fast component is attributed to a trapped-electron and a free-hole recombination, and the slow component is attributed to trapped electron-hole recombination. The activation energies for the process of diffusion of trapped electrons from their Ti3+ trapping sites are estimated.     

Light-induced charge separation in anatase TiO2 particles

Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2).     

Hole-trapping effect on thermoelectric power of mixed ionic electronic conductor BaTiO3

The effect of hole-trapping on the thermopower of a mixed ionic electronic conductor, e.g., BaTiO3, is analyzed in terms of irreversible thermodynamics by taking trapped holes as a fourth kind of electronic charge carrier in addition to free electrons, free holes and mobile oxide ions. It is found that the effect manifests itself in two ways: thermostatically in the ionic thermopower via the thermodynamic factor and dynamically in the electronic thermopower via the electrical conductivity contribution of the trapped holes. The thermopowers of both 99.995% pure, undoped and 1.8 m/o Al-doped BaTiO3, that were measured against oxygen activity in the range of -18 < log aO2 < or = 0 at elevated temperatures of 800 degrees to 1100 degrees C [H.-I. Yoo and C. R. Song, J. Electroceram., 2001, 6, 61, ref. 6], are reanalyzed by taking into account the hole-trapping for the doped case. It is found that while the reduced heats-of-transport of free electrons and holes are, respectively, close to their thermal energy k(B)T (k(B) being the Boltzmann constant), that of trapped holes is close to their migration energy that is essentially the same as the trapping energy onto the acceptors doped, 1.04 eV.     

Inhibition of Electron-Hole Recombination in Substitutionally Doped Colloidal Semiconductor Crystallites

The subtitutional doping of 120-Å- sized TiO₂ Particles with Fe( III )ions has a profound effect on the charge carrier recombination time in this colloidal semiconductor. In undoped particles, the mean lifetime of an electronhole pair is ca. 30 ± 15 ns. Doping with 0.5% Fe( III ) drastically augments the charge-carrier lifetime which is extended to minutes or hours. The slow character of the recombination dynamics in Fe( III )-doped colloids was confirmed by laser photolysis using the characteristic optical of electrons in TiO₂ to monitor the time course of the reaction. EPR studies showed the Fe( III ) ions to enter the host lattice on Ti( IV ) sites, charge compensation taking place through the formation of oxygen vacancies. Valence-band holes produced under band-gap excitation react with these centers it the bulk forming Fe( IV ), the conduction band electrons being trapped by Ti( IV ) at the particle surface. Presumably, the spatial separation of the trapped electron and hole sites inhibits their recombination.     

In Situ Observation of Hot Carrier Transfer at Plasmonic Au/Metal-Organic Frameworks (MOFs) Interfaces

Constructing heterostructures have been demonstrated as an ideal strategy for boosting charge separation on plasmonic photocatalysts, but the detailed interface charge transfer mechanism remains elusive. Herein, that authors fabricate plasmonic Au and metal-organic frameworks (MOFs, NH₂−MIL-125 and MIL-125 used in this work) heterostructures and explore the interface charge transfer mechanism by in situ electron paramagnetic resonance (EPR) spectroscopy and electrochemical measurements. The plasmon-excited hot electrons on Au can transfer across the Au/MOF interface and be captured by the coordinatively unsaturated sites of secondary building units (Ti₈O₈(OH)₄ cluster) of the MOF structure, and the plasmon-excited hot holes on Au tend to transfer to and be trapped at the functionalized organic ligand (1,4-benzenedicarboxylate−NH₂). The spatially separated hot electrons and holes exhibit boosted the photocatalytic activity for chromium (VI) reduction and selective benzyl alcohol oxidation. This work illustrates the advantage of the versatile functionalization of MOF structures enabling molecular-level manipulation of interface charge transfer on plasmonic photocatalysts.     

Electron and hole transport to trap groups at the ends of conjugated polyfluorenes

Polyfluorenes (pF) were synthesized having anthraquinone (AQ) or naphtylimide (NI) end caps that trap electrons or di- p-tolylaminophenyl (APT2) caps that trap holes. The average lengths of the pF chains in these molecules varied from 7 to 30 nm. End capping was found not to be complete in these molecules so that some were without caps. Electrons or holes were injected into these polymers in solution by pulse radiolysis. Following attachment, the charges migrated to the end cap traps in times near 2 ns in pF12AQ or 5 ns in pF35NI. From these observations, electron mobilities for transport along single chains to the end caps in THF solution were determined to be smaller by a factor of 100 than those observed by microwave conductivity. Despite this, the mobilities were sufficiently large to provide encouragement to the use of such single chains in solar photovoltaics. Most charges were observed to transport over substantial distances in these polymers, but 23, 18, and 37% of the charges attached to pFNI, pFAQ, and pFAPT2, respectively, were trapped in the pF chains and decayed by slower bimolecular reactions. For pFAQ and pFAPT2, all of the trapped charges were accounted for by estimates of the fraction of molecules having no end cap traps. For pF35NI, 23% of the attached electrons were found to be trapped in the chains, but only 4% of chains were expected to have no end caps. This could indicate some trapping by kinks or other defects but may just reflect uncertainties in the capping of this long polymer. When the charges reach the trap groups, their spectra have no features of pF(*-) or pF(*+), nor do the principal bands of the trapped ions resemble spectra of the radical ions of isolated trap molecules. The optical absorption spectra are rather dominated by new bands identified as charge-transfer transitions, which probably reinject electrons or holes into the pF chains. The energies of those bands correlate well with measured redox potentials.     

Dynamics of efficient electron-hole separation in TiO2 nanoparticles revealed by femtosecond transient absorption spectroscopy under the weak-excitation condition

The transient absorption of nanocrystalline TiO(2) films in the visible and IR wavelength regions was measured under the weak-excitation condition, where the second-order electron-hole recombination process can be ignored. The intrinsic dynamics of the electron-hole pairs in the femtosecond to picosecond time range was elucidated. Surface-trapped electrons and surface-trapped holes were generated within approximately 200 fs (time resolution). Surface-trapped electrons, which gave an absorption peak at around 800 nm, and bulk electrons, which absorbed in the IR wavelength region, decayed with a 500-ps time constant due to relaxation into deep bulk trapping sites. It is already known that, after this relaxation, electrons and holes survive for microseconds. We interpreted these long lifetimes in terms of the prompt spatial charge separation of electrons in the bulk and holes at the surface.     

A bioinspired construct that mimics the proton coupled electron transfer between P680*+ and the Tyr(Z)-His190 pair of photosystem II

A bioinspired hybrid system, composed of colloidal TiO2 nanoparticles surface modified with a photochemically active mimic of the PSII chlorophyll-Tyr-His complex, undergoes photoinduced stepwise electron transfer coupled to proton motion at the phenolic site. Low temperature electron paramagnetic resonance studies reveal that injected electrons are localized on TiO2 nanoparticles following photoexcitation. At 80 K, 95% of the resulting holes are localized on the phenol moiety and 5% are localized on the porphyrin. At 4.2 K, 52% of the holes remain trapped on the porphyrin. The anisotropic coupling tensors of the phenoxyl radical are resolved in the photoinduced D-band EPR spectra and are in good agreement with previously reported g-tensors of tyrosine radicals in photosystem II. The observed temperature dependence of the charge shift is attributed to restricted nuclear motion at low temperature and is reminiscent of the observation of a trapped high-energy state in the natural system. Electrochemical studies show that the phenoxyl/phenol couple of the model system is chemically reversible and thermodynamically capable of water oxidation.     

Sm-doped g-C_3N_4/Ti_3C_2 MXene heterojunction for visible-light photocatalytic degradation of ciprofloxacin

A heterojunction of Sm-doped g-C_3N_4/Ti_3C_2 MXene(SCN/MX) was constructed via prepolymerization and solid mixture-calcination method.The modified g-C_3N_4 presented a hollow porous seaweed-like shape which can increase its specific area and active sites.In SCN/MX composite,the optical properties,no matter optical absorption ability or separation performance of photo-induced electrons and holes,were enhanced.Among them,Sm-doping may play an important role on transferring the photogenerated electrons to suppress their recombination,and Ti_3C_2 MXene would broaden light absorption and further improve the carrier migration efficiency.The SCN/MX presented higher photocatalytic degradation efficiency( 99%) of cipro floxacin under visible light irradiation.The quenching experiments and electron spin-resonance spectroscopy confirmed that the dominated active materials were superoxide radical and holes.The degradation mechanisms of ciprofloxacin(CIP) over the SCN/MX were attacking of the active materials on the piperazine ring and quinolone ring,and the final products were CO_2,H_2O and F~-.     

Recombination rate constant of free electrons and holes in thin CdSe films

The decay kinetics of electrons generated in thin CdSe films by laser pulse (wavelength 337 nm, pulse duration 8 ns) at 295 K was studied by the microwave photoconductivity method (36 GHz). Based on analysis of the photoresponse decay kinetics and the reactions of free and trapped electrons, holes, and ions, a model for the processes was proposed and the recombination rate constant of free electrons and holes in cadmium selenide was determined, being (4–6)· 10–11 cm³ s⁻¹. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 740–743, May, 2006. The samples were kindly presented by Yu. V. Meteleva.     

Intraband relaxation in CdSe nanocrystals and the strong influence of the surface ligands

The intraband relaxation between the 1Pe and 1Se state of CdSe colloidal quantum dots is studied by pump-probe time-resolved spectroscopy. Infrared pump-probe measurements with approximately 6-ps pulses show identical relaxation whether the electron has been placed in the 1Se state by above band-gap photoexcitation or by electrochemical charging. This indicates that the intraband relaxation of the electrons is not affected by the photogenerated holes which have been trapped. However, the surface ligands are found to strongly affect the rate of relaxation in colloid solutions. Faster relaxation (<8 ps) is obtained with phosphonic acid and oleic acid ligands. Alkylamines lead to longer relaxation times of approximately 10 ps and the slowest relaxation is observed for dodecanethiol ligands with relaxation times approximately 30 ps. It is concluded that, in the absence of holes or when the holes are trapped, the intraband relaxation is dominated by the surface and faster relaxation correlates with larger interfacial polarity. Energy transfer to the ligand vibrations may be sufficiently effective to account for the intraband relaxation rate.     

Photochemical generation of electrons and holes in germanium-containing ITQ-17 zeolite

Laser flash photolysis of germanium-containing ITQ-17 zeolite (Ge/ITQ-17, a single polymorph of beta zeolite) at 266 nm generates a transient spectrum decaying in the sub-millisecond time scale that is compatible with the formation of two transient species. The shorter lived transient (tau approximately 45 micros under nitrogen) has been assigned to trapped electrons due to the characteristic spectroscopic absorption (single band at 480 nm) and its quenching by typical electron scavengers such as N(2)O and CH(2)Cl(2). The second longer lived transient (lambda(max) = 500, 540, and 600 nm; tau approximately 390 micros) is not quenched by O(2) or electron scavengers, but it is quenched by methanol as hole scavenger and has been assigned to positive holes. Also there is a remarkable similarity of the transient spectrum of the Ge/ITQ-17 with the optical spectrum reported previously for electron-hole pairs in ZSM-5 zeolite. Under the same irradiation conditions, photoejection of electrons and photogeneration of positive holes has not been observed for conventional aluminosilicate zeolites, all-silica zeolites, or GeO(2)-impregnated zeolites. Therefore this photochemical behavior has been ascribed to the presence of framework germanium atoms opening the way for photoresponsive zeolites. The ability of Ge/ITQ-17 to generate photochemically electrons and holes has been confirmed by adsorbing naphthalene and propyl viologen sulfonate as electron donor and acceptor, respectively, and observing the generation of the corresponding radical ions.     

聚合物单原子光催化剂的载流子分离和表面反应机制

近10年来, 研究者制备了大量的单原子催化剂(SACs), 其在光、 电、 热等催化体系中展现出优异的催化性能及较高的实用性和经济性. 光催化过程的独特性使其在催化本质上明显不同于热催化和电催化过程, 即处于激发态的电子和空穴参与反应, 而非基态的价电子. 本文首先探讨了有机聚合半导体与传统无机金属化合物半导体的区别, 指出聚合物半导体介电常数通常较小且光生电子与空穴的中心距离过短(计算上通常 ^{<1 nm), 导致其界面处几乎不存在明显的能带弯曲. 将金属离子引入聚合物半导体的骨架中可以有效引入给体-受体对, 在提高载流子分离效率的同时延长其寿命. 在高效聚合物基单原子光催化剂的设计过程中, 引入单原子金属位点后的激发态电荷分布及捕获态电子对反应的驱动力是决定催化剂整体性能的关键因素. 时间-空间双因子布局分析法和瞬态吸收光谱可为研究者提供相关信息. 随着人工智能的进一步发展, 建立回归精度接近或达到密度泛函理论水准的能量函数, 从而反推激发态下体系的能量变化, 有望为光催化反应的激发特性与反应活性建立可靠的联系. 此外, 配体和溶剂化效应在今后的研究中也应被仔细考虑.}     

石墨烯膜质子传输巨大光效应的微观机理

Graphene monolayers are permeable to thermal protons and impermeable to other atoms and molecules, exhibiting their potential applications in fuel cell technologies and hydrogen isotope separation. Furthermore, the giant photoeffect in proton transport through catalytically activated graphene membranes was reported by Geim et al. Their experiment showed that the synergy between illumination and the catalytically active metal plays a key role in this photoeffect. Geim et al. suggested that the local photovoltage created between metal nanoparticles and graphene could funnel protons and electrons toward the metal nanoparticles for the production of hydrogen, while repelling holes away from them, causing the giant photoeffect. However, based on static electric field theory, this explanation is not convincing and the work lacks an analysis on the microscopic mechanism of this effect. Herein, we provide the exact microscopic mechanism behind this phenomenon. In semi-metal pristine graphene, most photon excited hot electrons relax to lower energy states within a timescale of 10⁻¹² s, while the typical timescale of a chemical reaction is 10⁻⁶ s. Thus, hot electrons excited by incident photons relax to lower energy states before reacting with protons through the graphene. When graphene is decorated with metal, electron transfer between the graphene and the metal, induced by different work functions, would result in the formation of interface dipoles. When using metals such as Pt, Pd, Ni, etc., which can strongly interact with graphene, local dipoles form. Protons are trapped around the negative poles of the local dipoles, while electrons are around the positive poles. Upon illumination, the electrons are excited to metastable excited states with higher energy levels. Due to the energy barriers around them, the free electrons in the metastable excited states will have a relatively longer lifetime, which facilitates the production of hydrogen through their effective reaction with protons that permeated through the graphene. The concentration of high-energy electrons under illumination was estimated, and the results showed that more electrons are energized to the excited state with strong illumination. According to the analysis, the giant photoeffect in proton transport through the catalytically activated graphene membrane is attributed to long-lived hot electrons and a fast proton transport rate. Since there is no change in the activation energy of the reaction, the metal catalyst increases the rate of the reaction by increasing the number of successful collisions between the reactants to produce the significant photoeffect. This might lead to a new microscopic mechanism that clarifies the role of the catalyst in improving the efficiency of photo(electro)catalytic reactions.     

Inside powders: a theoretical model of interfaces between MgO nanocrystallites

The electron- and hole-trapping and optical properties of a wide variety of interfaces between MgO nanocrystallites are investigated for the first time using a quantum-mechanical embedded-cluster method and time-dependent density functional theory. We conclude that delocalized holes can be transiently trapped at a large number of places within a powder. However, it is more energetically favorable for holes to trap on low-coordinated anions on the nanocrystallite surface, forming O- species. Electrons are trapped at few interfaces but are readily trapped by surface kink and corner sites. Contrary to common perception, our calculations of optical absorption spectra indicate that a variety of features buried within a powder can be exited with photon energies less than 5 eV, usually used to selectively excite low-coordinated surface sites.     

Using pulse shape discrimination to sort individual energy deposition events in a germanium crystal

A fast digital oscilloscope based pulse shape discrimination (PSD) system has been tested with intrinsic germanium detectors large enough to allow ionizing events which generate localized electron-hole pairs at a single site to be segregated from those depositing energy at several different sites in the crystal. Drift velocities of the electrons and holes result in pulses several hundred nanoseconds long. Since the electric field varies by almost a factor of 10 between the outer and inner surfaces, collection of electrons and holes can frequently be dinstinguished, and pulses due to multi-site events can be distinguished from single site events.     

Electrontransfer through DNA and metal-containing DNA

DNA is currently explored as a new material for functional, molecular nano-architectures. In this respect, one major question is to transform DNA into a conducting material which has the potential for self-assembly into electronically active networks. The article covers recent insight into how DNA transports positive (holes) and negative (excess electrons) charges. It was found that holes move through DNA over significant distances using a G- and to a lesser extent also A-based hopping mechanism. EPR studies and recent investigations with model systems show that excess electrons can also hop through the duplex. The second part of the article describes how DNA is currently modified, particularly coated with metals, in order to increase the conductivity.