Probing electromechanical behaviors by datacube piezoresponse force microscopy in ambient and aqueous environments.

For assisting the in-depth investigations of widespread electromechanical phenomena in functional materials, piezoresponse force microscopy (PFM) has gradually evolved to realize full information-flow acquisition and fit the conductive liquid working environments. Here, we designed data cube (DCUBE) based PFM to collect the electromechanical effect into a high-dimensional array of piezoresponse by adding ac bias with a wide range of frequencies to the probe. The electromechanical and mechanical spectra can be consecutively extracted at each pixel in the intermittent-contact mode. High-resolution ferroelectric domains of the poled LiNbO3 were mapped, corresponding to the ideal phase contrasts of about 180° in air, decane, and deionized water. Rich information detection and non-contact mode in DCUBE-PFM bring many merits on the electromechanical characterizations, especially for elastic-inhomogeneous surfaces and soft materials. Moreover, we systematically reveal the Debye screening effect and time-resolved field-oriented ion dynamics, which play crucial roles in the reduction of PFM spatial resolution in electrolytes. These physical discussions provide strategies to further realize high-resolution electromechanical imaging in highly conductive liquid environments.

Strain-Induced Lithium Losses in the Solid Electrolyte Interphase on Silicon Electrodes.

The chemical and mechanical stability of SEI layers are particularly important for high capacity anode materials such as silicon, which undergoes large volume changes (∼300%) during cycling. In this work, we present a novel approach for applying controlled strains to SEI films with patterned Si electrodes to systematically investigate the impact of large volume changes on SEI formation and evolution. Comparisons between patterned silicon islands and continuous silicon thin films make it possible to correlate the irreversible capacity losses due to expansion and contraction of underlying silicon. The current work demonstrates that strain in the SEI layer leads to more lithium consumption. The combination of in situ AFM and electrochemical lithium loss measurements provides further information on SEI layer growth. These experiments indicate that in-plane strains in the SEI layer lead to substantial increases in the amount of inorganic phase formation, without significantly affecting the overall SEI thickness. These observations are further supported with EIS and TOF-SIMS results. A map of irreversible capacity evolution with strain in the SEI is obtained from the experimental results.

Nanoelectrical and Nanoelectrochemical Imaging of Pt/p-Si and Pt/p+ -Si Electrodes.

The interfacial properties of electrolessly deposited Pt nanoparticles (Pt-NPs) on p-Si and p+ -Si electrodes were investigated on the nanometer scale using a combination of scanning probe methods. Atomic force microscopy (AFM) showed highly dispersed Pt-NPs with diameters of 20-150 nm on the Si surface. Conductive AFM measurements showed that only approximately half of the particles exhibited measurable contact currents, with a factor of 103 difference in current observed between particles at a given bias. Local current-voltage measurements revealed a rectifying junction with a resistance ≥10 MΩ at the Pt-NP/p-Si interface, whereas the Pt-NP/p+ -Si samples formed an ohmic junction with a local resistance ≥1 MΩ. The particles were strongly attached to the sample surface in air. However, in an electrolyte, the adhesion of the particles to the surface was substantially lower, and most of the particles had tip-contact currents that varied by a factor of approximately 10. Scanning electrochemical microscopy (SECM) showed smaller but more uniform electrochemical currents for the particles relative to the currents observed by conductive AFM. In accord with the conductive AFM measurements, the SECM measurements showed conductance through the substrate for only a minority of the particles. These results suggest that the electrochemical performance of the electrolessly deposited Pt nanoparticles on Si can be ascribed to: 1) The high resistance of the contact between the particles and the substrate, 2) the low (<50 %) fraction of particles that support high currents, and 3) the low adhesion of the particles to the surface when in contact with the electrolyte.

Atomic force microscopy with nanoelectrode tips for high resolution electrochemical, nanoadhesion and nanoelectrical imaging.

Multimodal nano-imaging in electrochemical environments is important across many areas of science and technology. Here, scanning electrochemical microscopy (SECM) using an atomic force microscope (AFM) platform with a nanoelectrode probe is reported. In combination with PeakForce tapping AFM mode, the simultaneous characterization of surface topography, quantitative nanomechanics, nanoelectronic properties, and electrochemical activity is demonstrated. The nanoelectrode probe is coated with dielectric materials and has an exposed conical Pt tip apex of ∼200 nm in height and of ∼25 nm in end-tip radius. These characteristic dimensions permit sub-100 nm spatial resolution for electrochemical imaging. With this nanoelectrode probe we have extended AFM-based nanoelectrical measurements to liquid environments. Experimental data and numerical simulations are used to understand the response of the nanoelectrode probe. With PeakForce SECM, we successfully characterized a surface defect on a highly-oriented pyrolytic graphite electrode showing correlated topographical, electrochemical and nanomechanical information at the highest AFM-SECM resolution. The SECM nanoelectrode also enabled the measurement of heterogeneous electrical conductivity of electrode surfaces in liquid. These studies extend the basic understanding of heterogeneity on graphite/graphene surfaces for electrochemical applications.

Solar-Driven H2 O2 Generation From H2 O and O2 Using Earth-Abundant Mixed-Metal Oxide@Carbon Nitride Photocatalysts.

Light-driven generation of H2 O2 only from water and molecular oxygen could be an ideal pathway for clean production of solar fuels. In this work, a mixed metal oxide/graphitic-C3 N4 (MMO@C3 N4 ) composite was synthesized as a dual-functional photocatalyst for both water oxidation and oxygen reduction to generate H2 O2 . The MMO was derived from a NiFe-layered double hydroxide (LDH) precursor for obtaining a high dispersion of metal oxides on the surface of the C3 N4 matrix. The C3 N4 is in the graphitic phase and the main crystalline phase in MMO is cubic NiO. The XPS analyses revealed the doping of Fe(3+) in the dominant NiO phase and the existence of surface defects in the C3 N4 matrix. The formation and decomposition kinetics of H2 O2 on the MMO@C3 N4 and the control samples, including bare MMO, C3 N4 matrix, Ni- or Fe-loaded C3 N4 and a simple mixture of MMO and C3 N4 , were investigated. The MMO@C3 N4 composite produced 63 µmol L(-1) of H2 O2 in 90 min in acidic solution (pH 3) and exhibited a significantly higher rate of production for H2 O2 relative to the control samples. The positive shift of the valence band in the composite and the enhanced water oxidation catalysis by incorporating the MMO improved the light-induced hole collection relative to the bare C3 N4 and resulted in the enhanced H2 O2 formation. The positively shifted conduction band in the composite also improved the selectivity of the two-electron reduction of molecular oxygen to H2 O2 .

Exceptionally Long-Lived Charge Separated State in Zeolitic Imidazolate Framework: Implication for Photocatalytic Applications.

Zeolitic imidazolate frameworks (ZIFs) have emerged as a novel class of porous metal-organic frameworks (MOFs) for catalysis application because of their exceptional thermal and chemical stability. Inspired by the broad absorption of ZIF-67 in UV-vis-near IR region, we explored its excited state and charge separation dynamics, properties essential for photocatalytic applications, using optical (OTA) and X-ray transient absorption (XTA) spectroscopy. OTA results show that an exceptionally long-lived excited state is formed after photoexcitation. This long-lived excited state was confirmed to be the charge-separated (CS) state with ligand-to-metal charge-transfer character using XTA. The surprisingly long-lived CS state, together with its intrinsic hybrid nature, all point to its potential application in heterogeneous photocatalysis and energy conversion.

Transition Metal Substitution Effects on Metal-to-Polyoxometalate Charge Transfer.

A series of hetero-bimetallic transition metal-substituted polyoxometalates (TMSPs) were synthesized based on the Co(II)-centered ligand [Co(II)W11O39](10-). The eight complex series, [Co(II)(M(x)OHy)W11O39]((12-x-y)-) (M(x)OHy = V(IV)O, Cr(III)(OH2), Mn(II)(OH2), Fe(III)(OH2), Co(II)(OH2), Ni(II)(OH2), Cu(II)(OH2), Zn(II)(OH2)), of which six are reported for the first time, was synthesized starting from [Co(III)W11O39](9-) and studied using spectroscopic, electrochemical, and computational techniques to evaluate the influence of substituted transition metals on the photodynamics of the metal-to-polyoxometalate charge transfer (MPCT) transition. The bimetallic complexes all show higher visible light absorption than the plenary [Co(II)W12O40](6-) and demonstrate the same MPCT transition as the plenary complex, but they have shorter excited-state lifetimes (sub-300 ps in aqueous media). The decreased lifetimes are rationalized on the basis of nonradiative relaxation due to coordinating aqua ligands, increased interaction with cations due to increased negative charge, and the energy gap law, with the strongest single factor appearing to be the charge on the anion. The most promising results are from the Cr- and Fe-substituted systems, which retain excited-state lifetimes at least 50% of that of [Co(II)W12O40](6-) while more than tripling the absorbance at 400 nm.

Nanoscale optomechanical actuators for controlling mechanotransduction in living cells.

To control receptor tension optically at the cell surface, we developed an approach involving optomechanical actuator nanoparticles that are controlled with near-infrared light. Illumination leads to particle collapse, delivering piconewton forces to specific cell surface receptors with high spatial and temporal resolution. We demonstrate optomechanical actuation by controlling integrin-based focal adhesion formation, cell protrusion and migration, and T cell receptor activation.

Efficient water-splitting device based on a bismuth vanadate photoanode and thin-film silicon solar cells.

A hybrid photovoltaic/photoelectrochemical (PV/PEC) water-splitting device with a benchmark solar-to-hydrogen conversion efficiency of 5.2% under simulated air mass (AM) 1.5 illumination is reported. This cell consists of a gradient-doped tungsten-bismuth vanadate (W:BiVO4 ) photoanode and a thin-film silicon solar cell. The improvement with respect to an earlier cell that also used gradient-doped W:BiVO4 has been achieved by simultaneously introducing a textured substrate to enhance light trapping in the BiVO4 photoanode and further optimization of the W gradient doping profile in the photoanode. Various PV cells have been studied in combination with this BiVO4 photoanode, such as an amorphous silicon (a-Si:H) single junction, an a-Si:H/a-Si:H double junction, and an a-Si:H/nanocrystalline silicon (nc-Si:H) micromorph junction. The highest conversion efficiency, which is also the record efficiency for metal oxide based water-splitting devices, is reached for a tandem system consisting of the optimized W:BiVO4 photoanode and the micromorph (a-Si:H/nc-Si:H) cell. This record efficiency is attributed to the increased performance of the BiVO4 photoanode, which is the limiting factor in this hybrid PEC/PV device, as well as better spectral matching between BiVO4 and the nc-Si:H cell.

Unraveling the exciton quenching mechanism of quantum dots on antimony-doped SnO2 films by transient absorption and single dot fluorescence spectroscopy.

Integrating quantum dots (QDs) into modern optoelectronic devices requires an understanding of how a transparent conducting substrate affects the properties of QDs, especially their excited-state dynamics. Here, the exciton quenching dynamics of core/multishell (CdSe/CdS(3ML)ZnCdS(2ML)ZnS(2ML)) quantum dots deposited on glass, tin oxide (SnO2), and antimony (Sb)-doped tin oxide (ATO) films are studied by transient absorption and single QD fluorescence spectroscopic methods. By comparing ensemble-averaged fluorescence decay and transient absorption kinetics, we show that, for QDs on SnO2, the exciton is quenched by electron transfer from the QD to SnO2. At the QD-ATO interface, much faster exciton quenching rates are observed and attributed to fast Auger recombination in charged QDs formed by Fermi level equilibration between the QD and n-doped ATO. Single QDs on SnO2 and ATO show similar blinking dynamics with correlated fluctuations of emission intensities and lifetimes. Compared to QDs on SnO2, QDs on ATO films show larger variation of average exciton quenching rates, which is attributed to a broad distribution of the number of charges and nature of charging sites on the QD surface.

Synthesis and characterization of a metal-to-polyoxometalate charge transfer molecular chromophore.

[P(4)W(35)O(124){Re(CO)(3)}(2)](16-) (1), a Wells-Dawson [α(2)-P(2)W(17)O(61)](10-) polyoxometalate (POM)-supported [Re(CO)(3)](+) complex containing covalent W(VI)-O-Re(I) bonds has been synthesized and characterized by several methods, including X-ray crystallography. This complex shows a high visible absorptivity (ε(470 nm) = 4000 M(-1) cm(-1) in water) due to the formation of a Re(I)-to-POM charge transfer (MPCT) band. The complex was investigated by computational modeling and transient absorption measurements in the visible and mid-IR regions. Optical excitation of the MPCT transition results in instantaneous (<50 fs) electron transfer from the Re(I) center to the POM ligand.

Efficient light-driven carbon-free cobalt-based molecular catalyst for water oxidation.

The abundant-metal-based polyoxometalate complex [Co(4)(H(2)O)(2)(PW(9)O(34))(2)](10-) is a hydrolytically and oxidatively stable, homogeneous, and efficient molecular catalyst for the visible-light-driven catalytic oxidation of water. Using a sacrificial electron acceptor and photosensitizer, it exhibits a high (30%) photon-to-O(2) yield and a large turnover number (>220, limited solely by depletion of the sacrificial electron acceptor) at pH 8. The photocatalytic performance of this catalyst is superior to that of the previously reported precious-metal-based polyoxometalate water oxidation catalyst [{Ru(4)O(4)(OH)(2)(H(2)O)(4)}(γ-SiW(10)O(36))(2)](10-).

Insights into photoinduced electron transfer between [Ru(mptpy)2]4+ (mptpy = 4'(4-methylpyridinio)-2,2':6',2''-terpyridine) and [S2O8]2-: computational and experimental studies.

The mechanism and electron transfer dynamics of the reaction [Ru(II)(mptpy)(2)](4+) + hnu + [S(2)O(8)](2-) --> [Ru(III)(mptpy)(2)](5+) + SO(4)(2-) + SO(4)(-*) were studied using various computational (density functional and exciton interaction theories) and experimental (transient absorption, static and time-resolved fluorescence spectroscopy, and other) techniques. The results were compared with those recently reported for [Ru(bpy)(3)](2+) dye [ref 18]. It was found that the excitation energy of [Ru(mptpy)(2)](4+) is about 0.4-0.5 eV smaller than that of [Ru(bpy)(3)](2+), which is consistent with the measured absorption maxima of 445 and 507 nm, for [Ru(bpy)(3)](2+) and [Ru(mptpy)(2)](4+), respectively. The smaller excitation energy in [Ru(mptpy)(2)](4+) correlates with much slower electron transfer rates to persulfate compared to [Ru(bpy)(3)](2+). The quenching of the photoexcited [Ru(mptpy)(2)](4+) by [S(2)O(8)](2-) occurs via a unimolecular mechanism with formation of a weak ion-pair complex {[Ru(mptpy)(2)](4+)...([S(2)O(8)](2-))(n)}, where n = 1 and 2. The initial photon is absorbed by the [Ru(mptpy)(2)](4+) fragment forming an MLCT state, e.g., the bright singlet state S1. This S1 state undergoes a fast spin-orbit coupling induced intersystem crossing to a lower-lying triplet and rapid subsequent relaxation down to the lowest triplet T1 via internal conversion and collisions with solvent molecules. At this stage, the electron transfer from [Ru(mptpy)(2)](4+) to a loosely attached [S(2)O(8)](2-) occurs in a dark reaction via elongation of the O-O peroxo bond of the oxidant [S(2)O(8)](2-). The electron transfer lifetimes in water are calculated to be 1/kappa(1) = 199.4 ns and 1/kappa(2) = 108.4 ns, for the 1:1 and 1:2 complexes, respectively. The computed electron transfer lifetimes (1/kappa(1)) are in reasonable agreement with their experimental values of 298 and 149 ns for the 1:1 and 1:2 complexes, respectively. The effect of solvent polarity on electron transfer rates is found to be significant: the less polar acetonitrile slows the rate by an order of magnitude compared to water.

Cs(9)[(gamma-PW(10)O(36))(2)Ru(4)O(5)(OH)(H(2)O)(4)], a new all-inorganic, soluble catalyst for the efficient visible-light-driven oxidation of water.

The tetraruthenium-substituted polyoxometalate Cs(9)[(gamma-PW(10)O(36))(2)Ru(4)O(5)(OH)(H(2)O)(4)] was synthesized and structurally, spectroscopically and electrochemically characterized; it was shown to be a catalyst for visible-light-induced water oxidation.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

Insights into photoinduced electron transfer between [Ru(bpy)(3)](2+) and [S(2)O(8)](2-) in water: computational and experimental studies.

We examine the mechanism of electron transfer between [Ru(bpy)(3)](2+) and [S(2)O(8)](2-) in aqueous solutions using time-dependent density functional and transition charge density model levels of theory. The calculations support the existence of a short-lived, optically bright S1 state that decays to lower-lying triplet states T1 and T2. The T1 state leads to the charge transfer products, that is, [Ru(bpy)(3)](3+) + SO(4)(-*) + SO(4)(2-). It was shown that photoinduced (in the 420-520 nm wavelength range) electron transfer between [Ru(bpy)(3)](2+) and [S(2)O(8)](2-) may proceed via both the "unimolecular" and "bimolecular" pathways, in agreement with the previous experimental findings. This distinction arises on the basis of a weak interaction between the two reactants. Analysis of excited electronic states and their spin-orbit mixing suggests that a photon excites a MLCT S1 state of [Ru(bpy)(3)](2+)*/{[Ru(bpy)(3)](2+)...[S(2)O(8)](2-)}* that converts to the lower-lying T2 state via spin-orbit interaction, which is an intermediate in the S1 --> T2 --> T1 chain. Once the system has converted to T1, it can evolve toward charge transfer from [Ru(bpy)(3)](2+)* to [S(2)O(8)](2-) via elongation of the peroxo O-O bond that brings the "zero order" states of the [Ru(bpy)(3)](2+)* and [S(2)O(8)](2-) fragments into (near) resonance. An exciton interaction model in combination with the transition charge density model provides excellent agreement with TD-DFT and allows us to obtain insight into the electron transfer process. The steady-state luminescence studies of the quenching of [Ru(bpy)(3)](2+)* in aqueous solutions by [S(2)O(8)](2-) at pH 7.2 and 20 mM sodium phosphate buffer, the exact conditions used in our previous study of water oxidation [Geletii, Y. V.; Huang, Z. Q.; Hou, Y.; Musaev, D. G.; Lian, T. Q.; Hill, C. L. J. Am. Chem. Soc. 2009, 131, 7522-7523], show that 61% of the [Ru(bpy)(3)](2+) forms a ground state ion-pair complex [Ru(bpy)(3)](2+)...[S(2)O(8)](2-), and the unimolecular ET rate is 2.5 times faster than for the bimolecular process. The concentration of the ion-pair complexes decreases at higher sodium phosphate buffer.

Homogeneous light-driven water oxidation catalyzed by a tetraruthenium complex with all inorganic ligands.

A totally homogeneous, molecular, visible-light-driven water oxidation system is reported. The three system components are (i) a water oxidation catalyst, 1 (a Ru(IV)(4)O(4) cluster stabilized by oxidatively resistant [SiW(10)O(32)](8-) ligands); (ii) a photosensitizer, [Ru(bpy)(3)](2+); and (iii) a sacrificial electron acceptor, S(2)O(8)(2-). Dioxygen is formed rapidly with an initial turnover frequency of approximately 8 x 10(-2) s(-1) and an estimated quantum yield (defined as the number of O(2) molecules formed per two photons absorbed) of approximately 9%.

Photoinduced ultrafast electron transfer from CdSe quantum dots to Re-bipyridyl complexes.

Ultrafast dissociation of excitons in CdSe quantum dots via electron transfer to adsorbed Re-bipyridyl complexes was demonstrated. The dissociation pathway was determined by the observation of reduced adsorbate using femtosecond IR spectroscopy. The rate of electron transfer was shown to increase at smaller QD sizes. Electron transfer time as fast as 2.3 ps was observed, faster than the exciton annihilation time in CdSe. The ultrafast charge separation in this quantum dot-adsorbate donor-acceptor complex provides a potential approach for separating multiple excitons in quantum dots.

Theoretical analysis of the potential distribution and transportation behavior of the ordered alkyl monolayer-silicon junction.

A theoretical approach to the determination of the potential distribution within an organic monolayer sandwiched metal-insulator-semiconductor junction has been proposed with two simplified models, e.g. static (capacitance) model and dynamic (resistance) model. Compared with the resistance model, the capacitance model has been confirmed to be more valid for determining the potential distribution of the system. Further, the transportation behavior of the system has been simulated with a modified electron-tunneling model.