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Understanding and manipulating the one half-reaction of photoinduced hole-oxidation to oxygen are of fundamental importance to design and develop an efficient water-splitting process. To date, extensive studies on oxygen evolution from water splitting have focused on visible-light harvesting. However, capturing low-energy photons for oxygen evolution, such as near-infrared (NIR) light, is challenging and not well-understood. This report presents new insights into photocatalytic water oxidation using visible and NIR light. WO 2 -WO 3 hybrid nanorods were in situ fabricated using a wet-chemistry route. The presence of metallic WO 2 strengthens light absorption and promotes the charge-carrier separation of WO 3 . The efficiency of the oxygen evolution reaction over noble-metal-free WO 2 -WO 3 hybrids was found to be significantly promoted. More importantly, NIR light (≥700 nm) can be effectively trapped to cause the photocatalytic water oxidation reaction. The oxygen evolution rates are even up to around 220 (λ = 700 nm) and 200 (λ = 800 nm) mmol g -1 h -1 . These results demonstrate that the WO 2 -WO 3 material is highly active for water oxidation with low-energy photons and opens new opportunities for multichannel solar energy conversion.

Large-scale tetracene-doped anthracene nanowire arrays were prepared, and the doping effects were studied. The high doping concentration up to 10% (molar ratio) has been achieved, attributed to both the unique long-nanowire geometry and the excellent structural compatibility of anthracene and tetracene. The incorporation of long tetracene molecules into the matrix of short anthracene molecules induced an enlarged interlayer thickness, a decreased nanowire thickness, and an expanded nanowire width. The tetracene molecules were homogeneously embedded into the anthracene matrix at low doping concentrations (<1%). The doping became inhomogeneous at high doping concentrations (≥1%). The energy transfer efficiency between anthracene and tetracene is nearly 100% at doping concentrations ≥1%.

We have prepared photosensitizer-doped conjugated polymer nanoparticles by using a reprecipitation method. The conjugated polymer, poly[9,9-dibromohexylfluorene-2,7-ylenethylene-alt-1,4-(2,5-dimethoxy)phenylene] (PFEMO), was used as the host matrix to disperse tetraphenylporphyrin (TPP). These TPP-doped PFEMO nanoparticles are stable and have a uniform size of ∼50 nm. Efficient intraparticle energy transfer from PFEMO to TPP has been observed. The TPP emission of the nanoparticles was found to be enhanced by 21-fold by PFEMO under two-photon excitation. Enhanced two-photon excitation singlet oxygen generation efficiency in the TPP-doped PFEMO nanoparticles has been demonstrated. Our results suggest that these photosensitizer-doped conjugated polymer nanoparticles can act as novel photosensitizing agents for two-photon photodynamic therapy and related applications.

Novel multifunctional nanoparticles that combine two functionalities (a gold nanorod core and a porphyrin-doped mesoporous silica shell) into one entity were synthesized. Due to the encapsulation of mesoporous silica, the porphyrin can be well protected against the external bioenvironment. In addition, the generated singlet oxygen by porphyrin molecules can be easily released from the silica. We have demonstrated that these multifunctional nanoparticles can generate singlet oxygen with relatively higher yield compared to free porphyrin. These multifunctional nanocomposites are attractive candidates for simultaneous photosensitization and two-photon imaging as well as imaging guided therapy.

The process of benzene adsorption on an adjacent adatom-rest atom pair on Si(111)-7 x 7 at room temperature was studied using in-situ scanning tunneling microscopy (STM). Both adsorption and desorption of benzene were observed to take place mostly at adjacent sites during the process. DFT calculation results show that the bond length between the rest atom and the carbon atom in a pre-adsorbed benzene molecule increases due to the charge transfer from a neighboring rest atom in response to an approaching benzene molecule. Such increase in the bond length, when coupled resonantly to the C-Si thermal vibration, could result in bond breakage and desorption of the adsorbate. The studies provide evidence for the desorption of a chemisorbed benzene caused by an adsorbing benzene at a neighboring site through a substrate-mediated electronic interaction.

The adsorption of glycine and l-cysteine on Si(111)-7 x 7 was investigated using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). The observation of the characteristic vibrational modes and electronic structures of NH3+ and COO- groups for physisorbed glycine (l-cysteine) demonstrates the formation of zwitterionic species in multilayers. For chemisorbed molecules, the appearance of nu(Si-H), nu(Si-O), and nu(C=Omicron) and the absence of nu(O-H) clearly indicate that glycine and l-cysteine dissociate to produce monodentate carboxylate adducts on Si(111)-7 x 7. XPS results further verified the coexistence of two chemisorption states for each amino acid, corresponding to a Si-NH-CH2-COO-Si [Si-NHCH(CH2SH)COO-Si] species with new sigma-linkages of Si-N and Si-O, and a NH2-CH2-COO-Si [NH2CH(CH2SH)COO-Si] product through the cleavage of the O-H bond, respectively. Glycine/Si(111)-7 x 7 and l-cysteine/Si(111)-7 x 7 can be viewed as model systems for further modification of Si surfaces with biological molecules.

The attachment of methyl methacrylate (MMA) on Si(100)-2x1 was investigated using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) calculations. The HREELS spectra of chemisorbed MMA show the disappearance of characteristic vibrations of C=O (1725 cm(-1)) and C(sp(2))-H (3110, 1400, and 962 cm(-1)) coupled with the blue shift of the C=C stretching mode by 34 cm(-1) compared to those of physisorbed molecules. These results clearly demonstrate that both C=C and C=O in MMA directly participate in the interaction with the surface to form a SiCH(2)C(CH(3))=C(OCH(3))OSi species via a [4+2]-like cycloaddition. This binding configuration was further supported by XPS, UPS, and DFT studies.

The covalent binding of acetylethyne on Si(100)-2 x 1 has been investigated using high-resolution electron energy loss spectroscopy (HREELS) and X-ray photoelectron spectroscopy (XPS). The HREELS spectra of chemisorbed monolayers show the absence of the C=O, C[triple bond]C, and C(sp)-H stretching modes coupled with the appearance of C=C (at 1580 cm(-1)) and C(sp2)-H (at 3067 cm(-1)) stretching modes. This demonstrates that both of the C=O and CC groups of acetylethyne directly participate in binding with silicon surfaces to form C-O and C=C bonds, respectively, which is further confirmed by the XPS studies. A tetra-sigma-binding configuration through two [2 + 2]-like cycloaddition reactions in acetylethyne binding on Si(100) is proposed to account for the experimental observation. The cycloadduct containing a C=C double bond may be employed as an intermediate for further in situ chemical syntheses of multilayer organic thin films or surface functionalization.

We experimentally demonstrated that pyridine/Si(111)-7 x 7 can act as an electron donor/acceptor pair as a result of the charge transfer from the electron-rich N atom of pyridine to the electron-deficient adatom of the Si surface, evidenced by the upshift of 1.8 eV (state A) for the N(1s) core level upon the formation of a datively bonded complex compared to physisorbed molecules. Another state (B) whose N(1s) binding energy downshifts by 1.2 eV was assigned to an adduct through Si-C and Si-N covalent linkages, formed via a [4 + 2]-like addition mechanism on Si(111)-7 x 7. Binding molecules through the formation of the dative bond resulted from significant electron transfer opens a new approach for the creation of Si-based molecular architectures and modification of semiconductor interfacial properties with unsaturated organic molecules.