Samuel S. Mao

Semiconductor-based Photocatalytic Hydrogen Generation

2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Increasing Solar Absorption for Photocatalysis with Black Hydrogenated Titanium Dioxide Nanocrystals

An amorphous surface layer on titantium dioxide nanoparticles creates electronic states that allow longer-wavelength photoexcitation. When used as a photocatalyst, titanium dioxide (TiO2) absorbs only ultraviolet light, and several approaches, including the use of dopants such as nitrogen, have been taken to narrow the band gap of TiO2. We demonstrated a conceptually different approach to enhancing solar absorption by introducing disorder in the surface layers of nanophase TiO2 through hydrogenation. We showed that disorder-engineered TiO2 nanocrystals exhibit substantial solar-driven photocatalytic activities, including the photo-oxidation of organic molecules in water and the production of hydrogen with the use of a sacrificial reagent.

Nanomaterials for renewable energy production and storage

Over the past decades, there have been many projections on the future depletion of the fossil fuel reserves on earth as well as the rapid increase in green-house gas emissions. There is clearly an urgent need for the development of renewable energy technologies. On a different frontier, growth and manipulation of materials on the nanometer scale have progressed at a fast pace. Selected recent and significant advances in the development of nanomaterials for renewable energy applications are reviewed here, and special emphases are given to the studies of solar-driven photocatalytic hydrogen production, electricity generation with dye-sensitized solar cells, solid-state hydrogen storage, and electric energy storage with lithium ion rechargeable batteries.

Laser ablation in analytical chemistry - A review

Laser ablation is becoming a dominant technology for direct solid sampling in analytical chemistry. Laser ablation refers to the process in which an intense burst of energy delivered by a short laser pulse is used to sample (remove a portion of) a material. The advantages of laser ablation chemical analysis include direct characterization of solids, no chemical procedures for dissolution, reduced risk of contamination or sample loss, analysis of very small samples not separable for solution analysis, and determination of spatial distributions of elemental composition. This review describes recent research to understand and utilize laser ablation for direct solid sampling, with emphasis on sample introduction to an inductively coupled plasma (ICP). Current research related to contemporary experimental systems, calibration and optimization, and fractionation is discussed, with a summary of applications in several areas.

Properties of Disorder-Engineered Black Titanium Dioxide Nanoparticles through Hydrogenation

The recent discovery of “black” TiO2 nanoparticles with visible and infrared absorption has triggered an explosion of interest in the application of TiO2 in a diverse set of solar energy systems; however, what a black TiO2 nanoparticle really is remains a mystery. Here we elucidate more properties and try to understand the inner workings of black TiO2 nanoparticles with hydrogenated disorders in a surface layer surrounding a crystalline core. Contrary to traditional findings, Ti3+ here is not responsible for the visible and infrared absorption of black TiO2, while there is evidence of mid-gap states above the valence band maximum due to the hydrogenated, engineered disorders. The hydrogen atoms, on the other hand, can undergo fast diffusion and exchange. The enhanced hydrogen mobility may be explained by the presence of the hydrogenated, disordered surface layer. This unique structure thus may give TiO2, one of the most-studied oxide materials, a renewed potential.

Enabling silicon for solar-fuel production.

Ke Sun,† Shaohua Shen,*,‡,§ Yongqi Liang, Paul E. Burrows, Samuel S. Mao,* and Deli Wang*,†,⊥,# †Department of Electrical and Computer Engineering, Material Science Program, and QualComm Institute, University of California at San Diego, La Jolla, California 92093, United States ‡International Research Center for Renewable Energy, State Key Lab of Multiphase Flow in Power Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi 710049, China Department of Mechanical Engineering, University of California at Berkeley, Berkeley, California 94720, United States Department of Chemistry, Chemical Biological Center, Umea ̊ University, Linnaeus vag̈, 6 901 87 Umea,̊ Sweden Samuel Mao Institute of New Energy, Science Hall, 1003 Shangbu Road, Shenzhen, 518031, China

Femtosecond laser ablation ICP-MS

Femtosecond laser ablation was investigated for direct solid sample chemical analysis. The phonon relaxation time in a solid is of the order of 100 fs, which is the same as the laser pulse duration. For such excitation, there should be little time for the matrix to experience a “temperature” during the laser pulse. If the surface explodes before the photon energy is dissipated as heat in the lattice, the ablation process should produce stoichiometric vapor (elemental fractionation should be negligible). Based on this hypothesis, NIST glasses were ablated using 100 fs laser pulses at 800 nm, with subsequent elemental analysis using the ICP-MS. Pb and U intensities, and Pb/U ratios in the ICP, were measured during repetitively femtosecond-pulsed ablation. These data show that fluence (laser energy/spot area) has a significant influence on the amount of mass ablated and on the degree of fractionation. An optimal fluence was found at which the fractionation index approached unity; negligible fractionation. Infrared femtosecond laser ablation produced similar characteristics to UV nanosecond laser ablation.

A perspective on solar-driven water splitting with all-oxide hetero-nanostructures

A perspective on the design of all-oxide heterostructures for application in photoelectrochemical cells for solar water splitting is provided. Particular attention is paid to those structures which possess nanoscale feature dimensionality, as structures of this type are most likely to utilize the benefits afforded by the formation of oxide heterojunctions and likely to show functional behavior relating to the interfacial region. In the context of this discussion, a novel hetero-nanostructure array, based on quantum-confined and visible light-active iron(III) oxide nanostructures and their surface modification with tungsten(VI) oxide, is introduced. The heterostructure architecture is designed to combine the functionality of the consituent phases to address the primary requirements for electrodes enabling the efficient generation of hydrogen using solar energy: visible light activity, chemical stability, appropriate bandedge characteristics, and potential for low-cost fabrication. Photoelectrochemical characterization for solar hydrogen/oxygen generation indicates the presence of unexpected minority carrier transfer dynamics within the oxide hetero-nanostructures, as observed additionally by ultrafast transient absorption spectroscopy.

Delayed phase explosion during high-power nanosecond laser ablation of silicon

An important parameter for high-irradiance laser ablation is the ablation crater depth, resulting from the interaction of individual laser pulses on a targeted surface. The crater depth for laser ablation of single-crystal silicon shows a dramatic increase at a laser intensity threshold of approximately 2×1010 W/cm2, above which, large (micron-sized) particulates were observed to eject from the target. We present an analysis of this threshold phenomenon and demonstrate that thermal diffusion and subsequent explosive boiling after the completion of the laser pulse is a possible mechanism for the observed dramatic increase of the ablation depth. Calculations based on this delayed phase explosion model provide a satisfactory estimate of the measurements. In addition, we find that the shielding of an expanding mass plasma during laser irradiation has a profound effect on this threshold phenomenon.

Initiation of an early-stage plasma during picosecond laser ablation of solids

Picosecond time-resolved images of plasma initiation were recorded during pulsed-laser ablation of metal targets in an air atmosphere. An early-stage plasma was observed to form before the release of a material vapor plume. Close to the target surface, interferometry measurements indicate that the early-stage plasma has an electron number density on the order of 1020 cm−3. The longitudinal expansion of the ionization front for this plasma has a velocity 109 cm/s, during the laser pulse. In contrast, a material–vapor plume forms approximately 200 ps after the laser pulse, and it moves away from the target at 106 cm/s. The experimental observations of the early-stage plasma were simulated by using a theoretical model based on a two-fluids description of laser plasmas. The results indicate that the initiation of the plasma is due to air breakdown assisted by electron emission from the target.