This PDF file contains the front matter associated with SPIE Proceedings Volume 9935, including the Title Page, Copyright information, Table of Contents, Introduction (if any), and Conference Committee listing.

About 400 semiconductor solids are known to have photocatalytic activity for water splitting. Yet there is no single material that could satisfy all the requirements for desired photocatalysts: i) suitable band gap energy (1.7 eV< Eg < 2.3 eV) for high efficiency, ii) proper band position for reduction and/or oxidation of water, iii) long-term stability in aqueous solutions, iv) low cost, v) high crystallinity, and vi) high conductivity. Hence, in the selection of photocatalytic materials, we better start from intrinsically stable materials made of earth-abundant elements. The band bap energy is also the primary consideration to absorb ample amount of solar energy of wide wavelength spectrum. It sets the limit of theoretically maximum efficiency and it could also be extended by band engineering techniques. Upon selection of the candidate materials, we can also modify the materials for full utilization their potentials. The main path of efficiency loss in PEC water splitting process is recombination of photoelectrons and holes. We discuss the material designs including i) p-n heterojunction photoanodes for effective electron-hole separation, ii) electron highway to facilitate interparticle electron transfer, iii) metal or anion doping to improve conductivity of the semiconductor and to extend the range of light absorption, iv) one-dimensional nanomaterials to secure a short hole diffusion distance and vectoral electron transfer, and v) loading co-catalysts for facile charge separation. High efficiency has been demonstrated for all these examples due to efficient electron-hole separation. Finally, total systems for unassisted solar fuel production are demonstrated.

Designing new photocatalytic materials for improving photoconversion efficiency is a promising route to alleviate the steadily worsening environmental issues and energy crisis. Despite the invention of a large number of catalytic materials with well-defined structures, their overall efficiency in photocatalysis is still quite limited as the three key steps  light harvesting, charge generation and separation, and charge transfer to surface for redox reactions  have not been substantially improved. To improve each step in the complex process, there is a major trend to develop materials based on inorganic hybrid structures. In this case, interface engineering holds the promise for boosting the overall efficiency, given the key roles of interface structures in charge and energy transfer. In this talk, I will demonstrate several different approaches to designing inorganic hybrid structures with improved photocatalytic performance via interface engineering. The typical demonstrations include semiconductor-plasmonics systems for broad-spectrum light harvesting, metal-semiconductor interfaces for improved charge separation, semiconductor-MOF (metal-organic framework) configurations for activated surface reactions. It is anticipated that this series of works open a new window to rationally designing inorganic hybrid materials for photo-induced applications. References: (1) Bai, S.; Yang, L.; Wang, C.; Lin, Y.; Lu, J.; Jiang, J. and Xiong, Y.*, Angew. Chem. Int. Ed. 54, 14810-14814 (2015). (2) Bai, S.; Jiang, J.; Zhang, Q. and Xiong, Y.*, Chem. Soc. Rev. 44, 2893-2939 (2015). (3) Bai, S.; Li, X.; Kong, Q.; Long, R.; Wang, C.; Jiang, J. and Xiong, Y.*, Adv. Mater. 27, 3444-3452 (2015). (4) Bai, S.; Ge, J.; Wang, L.; Gong, M.; Deng, M.; Kong, Q.; Song, L.; Jiang, J.;* Zhang, Q.;* Luo, Y.; Xie, Y. and Xiong, Y.*, Adv. Mater. 26, 5689-5695 (2014). (5) Li, R.; Hu, J.; Deng, M.; Wang, H.; Wang, X.; Hu, Y.; Jiang, H. L.; Jiang, J.;* Zhang, Q.;* Xie, Y. and Xiong, Y.*, Adv. Mater. 26, 4783-4788 (2014).

Over the past decade, bismuth vanadate (BiVO4) has been intensely investigated as a promising photoanode material in photoelectrochemical (PEC) water splitting devices. However, little is known about native or impurity defects in this system, their effects on PEC performance, and possible passivation schemes. In this work, a detailed understanding of both the valence band and conduction band orbital character has been achieved using a combination of experimental and theoretical means. In particular, complimentary optical and X-ray spectroscopies, supported by density functional theory calculations, have been applied to high quality monoclinic BiVO4 thin films deposited by chemical vapor deposition, spin coating, and sputtering. The results demonstrate that the 2.5 eV bandgap is indirect with a higher lying 2.7 eV direct gap. Sub-bandgap radiative recombination is observed by temperature dependent photoluminescence measurements, which reveal the presence of a 620 meV deep trap. Annealing thin films of BiVO4 in a H2 atmosphere significantly reduces the sub-bandgap photoluminescence, which is correlated with an improvement by ~100-200 meV of the onset potential for photoanodic current, an increase of the fill factor, and elimination of photocurrent losses under frontside compared to backside illumination. These results on thin films, together with XPS of the thin films and solid state 1H NMR analysis of powders, suggest important parallel roles for hydrogen in BiVO4. We find that its substitutional incorporation at oxygen vacancy sites leads to passivation of associated deep level defects. In addition, interstitial hydrogen acts as a shallow level donor and beneficially increases conductivity in functional photoanodes. These results highlight that detailed understanding and controlling of carrier trapping in metal oxides, which often exhibit complex native defect properties due to compositional non-uniformities, provide significant opportunity for increasing PEC water splitting performance.

Most of the traditional photocatalytic hydrogen productions were conducted under room temperature. In this work, we selected nonplasmonic Pt metal anchored on TiO₂ nanoparticles with photothermal activity to explore more efficient hydrogen production technology over the whole solar spectrum. Photothermal experiments were carried out in a carefully designed top irradiated photocatalytic reactor that can withstand high temperature and relatively higher pressure. Four typical organic materials, i.e., methyl alcohol (MeOH), trielthanolamne (TEOA), formic acid (HCOOH) and glucose, were investigated. Formic acid, a typical hydrogen carrier, was found to show the best activity. In addition, the effects of different basic parameters such as sacrificial agent concentration and the temperature on the activity of hydrogen generation were systematically investigated for understanding the qualitative and quantitative effects of the photothermal catalytic reaction process. The hydrogen yields at 90 °C of the photothermal catalytic reaction with Pt/TiO₂ are around 8.1 and 4.2 times higher than those of reactions carried out under photo or thermal conditions alone. We can see that the photothermal hydrogen yield is not the simple sum of the photo and thermal effects. This result indicated that the Pt/TiO₂ nanoparticles can efficiently couple photo and thermal energy to more effectively drive hydrogen production. As a result, the excellent ability makes it superior to other conventional semiconductor photocatalysts and thermal catalysts. Future works could concentrate on exploring photothermal catalysis as well as the potential synergism between photo and thermal effects to find more efficient hydrogen production technology using the whole solar spectrum.

Publisher’s Note: This conference presentation, originally published on 3 November 2016, was withdrawn per author request.

Silicon is a promising contender in the race for low-bandgap absorbers for use in a solar driven monolithic water splitting cell (PEC). However, given its role as the low-bandgap material the silicon must sit behind the corresponding high-bandgap material and as such, it will be exposed to (red) light from the dry back-side – not from the wet front side, where the electrochemistry takes place.[1,2] Depending on the configuration of the selective contacts (junctions) this may lead to compromises between high absorption and low recombination.[2,3] We discuss the tradeoffs and compare modeling results to measurements. Regardless of configuration, the wet surface of the silicon is prone to passivation or corrosion and must therefore be carefully protected in service in order to remain active. We demonstrate the use of TiO2 as an effective protection layer for both photoanodes and photocathodes in acid electrolyte [4] and NiCoOx for photoanodes in alkaline electrolyte. [3] References: [1]: B. Seger et alia, Energ. Environ. Sci., 7 (8), 2397-2413 (2014), DOI:10.1039/c4ee01335b [2]: D. Bae et alia, Energ. Environ. Sci., 8 (2), 650-660 (2015), DOI: 10.1039/c4ee03723e [3]: D. Bae et alia, submitted, (2016) [4]: B. Mei et alia, J. Phys. Chem. C., 119 (27), 15019-15027 (2015), DOI: 10.1021/acs.jpcc.5b04407

The optical and electronic properties of TiO2 thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO2, critical challenges include the innate inability of TiO2 to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, we prepared ordered mesoporous TiO2 films co-modified by graphene quantum dot sensitization and nitrogen doping (GQD-N-TiO2) for hydrogen production from photoelectrochemical water splitting under visible light irradiation. First, cubic ordered mesoporous TiO2 films were prepared by a surfactant templated sol-gel method. Then, TiO2 films were treated with N2/Ar plasma for the incorporation of substitutional N atoms into the lattice of TiO2. GQDs were prepared by chemically oxidizing carbon nano-onions. The immobilization of GQDs was accomplished by reacting carboxyl groups of GQDs with amine groups of N-TiO2 developed by the prior immobilization of (3-aminopropyl)triethoxysilane (APTES). Successful immobilization of GQDs onto N-TiO2 was probed by UV-Vis, FT-IR, and scanning electron microscopy. Further, zeta potential and contact angle measurements showed enhanced surface charge and hydrophilicity, confirming the successful immobilization of GQDs. The GQD-N-TiO2, N-TiO2 and GQD-TiO2 films showed 400 times, 130 times and 8 times photocurrent enhancement, respectively, compared to TiO2 films for water splitting with a halogen bulb light source. This outstanding enhancement is attributed to the high surface area of mesoporous films and synergistic effects of nitrogen doping and GQD sensitization resulting in enhanced visible light absorption, efficient charge separation and transport.

In the focus of this study, mixtures of commercially available TiO₂ powders were created and their photocatalytic activity concerning the acetaldehyde degradation in the gas phase was tested. Further, the lifetime of the photogenerated charge carriers was analyzed by Laser-Flash-Photolysis-Spectroscopy. The acetaldehyde degradation experiments of the mixed powders lead to positive and negative deviations from the expected weighted mean. Nevertheless, their photocatalytic activity could be correlated with the lifetime of the charge carriers. A longer charge carrier lifetime at ambient conditions correlated with a lower fractional conversion of acetaldehyde. The advantageous activities of the samples were associated with a charge transfer reaction between larger and smaller particles comparable to the antenna mechanism.¹

Abstract: Including the shape and size effect, the controllable doping, hetero-composite and surface/interface are the prerequisite of colloidal nanocrystals for exploring their optoelectronic properties, such as fluorescence, plasmon-exciton coupling, efficient electron/hole separation, and enhanced photocatalysis applications. By controlling soft acid-base coordination reactions between cation molecular complexes and colloidal nanocrystals, we showed that chemical thermodynamics could drive nanoscale monocrystalline growth of the semiconductor shell on metal nano-substrates and the substitutional heterovalent doping in semiconductor nanocrystals. We have demonstrated evolution of relative position of Au and II-VI semiconductor in Au-Semi from symmetric to asymmetric configuration, different phosphines initiated morphology engineering, oriented attachment of quantum dots into micrometer nanosheets with synergistic control of surface/interface and doing, which can further lead to fine tuning of plasmon-exciton coupling. Therefore, different hydrogen photocatalytic performance, Plasmon enhanced photocatalysis properties have been achieved further which lead to the fine tuning of plasmon-exciton coupling. Substitutional heterovalent doping here enables the tailoring of optical, electronic properties and photocatalysis applications of semiconductor nanocrystals because of electronic impurities (p-, n-type doping) control. References: (1) J. Gui, J. Zhang*, et al. Angew. Chem. Int. Ed. 2015, 54, 3683. (2) Q. Zhao, J. Zhang*, etc., Adv. Mater. 2014, 26, 1387. (3) J. Liu, Q. Zhao, S. G. Wang*, J. Zhang*, etc., Adv. Mater. 2015, 27，2753-2761. (4) H. Qian, J. Zhang*, etc., NPG Asia Mater. (2015) 7, e152. (5) M. Ji, M. Xu, etc., J. Zhang*, Adv. Mater. 2016, in proof. (6) S. Yu, J. T. Zhang, Y. Tang, M. Ouyang*, Nano Lett. 2015, 15, 6282-6288. (7) J. Zhang, Y. Tang, K. Lee and M. Ouyang*, Science 2010, 327, 1634. (8) J. Zhang, Y. Tang, K. Lee, M. Ouyang*, Nature 2010, 466, 91.

A hybrid material that consists of a semiconductor and a binuclear metal complex having a redox photosensitizer and a catalytic unit was employed as a photocatalyst for CO₂ reduction under visible light. It was found that this kind of hybrid was capable of reducing CO₂ into HCOOH (or CO) according to two-step photoexcitation of the semiconductor and the photosensitizer unit of the metal complex. It was found that semiconductors of TaON, CaTaO₂N, C₃N₄, and Y-Ta oxynitride became active component for this system driven by visible light (λ > 400 nm) in combination with a binuclear Ru(II) complex.

A series of Ag-Pd/TiO2 catalysts have been prepared, characterized and tested for H2 production activities from water in the presence of organic sacrificial agents. The synergistic effect of metallic properties (plasmonic and Schottky mechanisms) was investigated. XPS results indicated that silver is present in the form of its oxides (Ag2O and AgO) at 0.2-0.4 wt. % loading while palladium is present as PdO and Pd metal at similar loading. However, metallic character for silver particles increases while that of palladium metal particles decreases with increasing their % in the investigated range (0-1 wt. %). HRTEM results coupled with EDX analyses indicated the presence of two types of Ag containing particles (large ones with about 4-6 nm and smaller ones with ca. 1nm in size). Palladium was only found forming Ag-Pd alloy/composite with a wide size distribution range between 10-60 nm. Both particles are composed of silver and palladium, however. Optimal photocatalytic H2 production rates were obtained for catalysts with a palladium to silver ratios between 4 and 1.5 in the case of bimetallic catalysts. In addition, H2 production rates showed linear dependency on plasmonic response of Ag. The study demonstrates that increased H2 production rates can be achieved from an understanding of plasmonic and Schottky properties of metals loaded on top of the semiconductor.

Photocatalytic overall water splitting into H₂ and O₂ is expected to be a promising method for the efficient utilization of solar energy. The design of optimal photocatalyst structures is a key to efficient overall water splitting, and the development of photocatalysts which can efficiently convert large portion of visible light spectrum has been required. Recently, a series of complex perovskite type transition metal oxynitrides, LaMg_xT _1-xO_1+3xN_2-3x, was developed as photocatalysts for direct water splitting operable at wide wavelength of visible light. In addition two-step excitation water splitting via a novel photocatalytic device termed as photocatalyst sheet was developed. This consists of two types of semiconductors (hydrogen evolution photocatalyst and oxygen evolution photocatalyst) particles embedded in a conductive layer, and showed high efficiency for overall water splitting. These recent advances in photocatalytic water splitting were introduced.

A new method to modify KCa₂Nb₃O₁₀ restacked nanohsheets with small Pt particle was developed, based on a simple electrostatic interaction between cationic precursor of Pt and negatively charged nanosheets. Compared to an ordinary impregnation method, the location of deposited Pt particles, size and valence state were different. More concretely, Pt was deposited not only on the external surface of the restacked KCa₂Nb₃O₁₀ nanohsheets, but also in the interlayer nanospace. Moreover, the deposited Pt was mainly very small (≤ 1 nm) and electron-deficient. The Pt deposited restacked KCa₂Nb₃O₁₀ nanosheets showed high photocatalytic activity for overall water splitting, which is the highest one among the nanosheets-based photocatalyst. The small particle size and deposition site of Pt are possible reasons for the high activity.

Photocatalytic conversion of carbon dioxide (CO2) to hydrocarbons such as methanol makes possible simultaneous solar energy harvesting and CO2 reduction. Our previous work is using graphene oxide (GO) as a promising photocatalyst for photocatalytic conversion of CO2 to methanol[1].When using graphene oxide as photocatalyst, the photocatalytic efficiency is 4-flod higher than TiO2 powder. GO has a lot of defects on the surface and those defects make sp2 carbon structure become sp3 carbon structure. The carbon structure change cause the GO has large energy gap about 2.7 eV to 3.2 eV. In order to remove the defect and reduce the energy gap of GO, Zhao et al. try to annealing GO powder in the nitrogen atmosphere at 900oC, the GO structure can be reduced to near graphene structure[2]. Zhu et al. do some low temperature annealing, it can control the structure and energy bandgap of GO by control annealing temperature. If the annealing temperature increase the bandgap of GO will be reduce[3]. So, we can using this annealing process to reduce the bandgap of the GO. In the varying temperature thermal reduction process, as the temperature increases from 130oC to 170oC, the functional groups of the graphene oxide will be reduced and band gap of graphene oxide will be narrowed at same time. The characteristic of thermal reduced graphene oxide were analyzed by SEM, XRD and Raman measurements. The band position was determined by UV/Vis. The reduction of functional groups correlates to red shift in light absorption and eventual quenching in the PL signal of RGOs. Combining hydrophobicity, light harvesting and PL quench, we get the highest yield of RGO150 (0.31 μmole g-1 -cat hr-1) is 1.7-fold higher than that of GO (0.18μmole g-1 -cat hr-1). This work investigates a modified method for using a thermal reduction process to reduce the energy gap of graphene oxide.

Band-offsets at BaTiO3/Cu2O heterojunction and enhanced photoelectrochemical response: theory and experiment Dipika Sharmaa, Vibha R. Satsangib, Rohit Shrivastava, Umesh V. Waghmarec, Sahab Dassa aDepartment of Chemistry, Dayalbagh Educational Institute, Agra-282 110 (India) bDepartment of Physics and Computer Sciences, Dayalbagh Educational Institute, Agra-282 110 (India) cTheoretical Sciences Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur, Bangalore-560 064 (India) * Phone: +91-9219695960. Fax: +91-562-2801226. E-mail: drsahabdas@gmail.com. Study on photoelectrochemical activity of pristine BaTiO3, Cu2O and BaTiO3/Cu2O heterojunction has been carried out using DFT based band offsets and charge carriers effective mass calculations and their experimental verification. The results of DFT calculations show that BaTiO3 and Cu2O have staggered type band alignment after the heterojunction formation and high mobility of electrons in Cu2O as compared to the electrons in BaTiO3. Staggered type band edges alignment and high mobility of electrons and holes improved the separation of photo-generated charge carriers in BaTiO3/Cu2O heterojunction. To validate the theoretical results experiments were carried out on pristine BaTiO3, Cu2O and BaTiO3/Cu2O heterojunction with varying thickness of Cu2O. All samples were characterized by X- Ray Diffractometer, SEM and UV–Vis spectrometry. Nanostructured thin films of pristine BaTiO3, Cu2O and BaTiO3/Cu2O heterojunction were used as photoelectrode in the photoelectrochemical cell for water splitting reaction. Maximum photocurrent density of 1.44 mA/cm2 at 0.90 V/SCE was exhibited by 442 nm thick BaTiO3/Cu2O heterojunction photoelectrode Increased photocurrent density and enhanced photoconversion efficiency, exhibited by the heterojunction may be attributed to improved conductivity and enhanced separation of the photogenerated carriers at the BaTiO3/Cu2O interface. The experimental results and first-principles calculations compare well, thus suggesting that such calculations have the potential to be used in screening various metal oxide heterojunction before performing the experiments thereby saving precious chemicals, time and energy. Keywords: Photoelectrochemical, Water splitting, heterojunction, Cu2O, BaTiO3 References: [1] Surbhi Choudhary, et al. Nanostructured bilayered thin films in photoelectrochemical water splitting - A review: International Journal of Hydrogen Energy, (2012). [2] Dipika Sharma, Anuradha Verma, V.R. Satsangi, Rohit shrivastav, Sahab Dass Nanostructured SrTiO3 thin films sensitized by Cu2O for Photoelectrochemical Hydrogen Generation. International journal of Hydrogen Energy;42:,4230-4241, 2014.

Energy is at the core of economic growth and development in the present day world. But relentless and unchecked use of harmful energy resources like fossil fuels (coil and oil), nuclear energy has taken a toll on mother nature. The energy coffers are being rapidly depleted and within a few years all of them will become empty, leaving nothing for the future generations to build on. Their constant usage has degraded the air quality and given way to land and water pollution. Scientists and world leaders have initiated a call for action to shift our dependence from currently popular energy sources to cleaner and renewable energy sources. Search for such energy sources have been going on for many years. Solar energy, wind energy, ocean energy, tidal energy, biofuel, etc. have caught the attention of people. Another such important which has become popular is 'Solar Hydrogen'. Many visionary scientists have called hydrogen the energy of the future. It is produced from water by direct or indirect use of sunlight in a sustainable manner. This paper discusses the current energy scenario, the importance of solar-hydrogen as a fuel and most importantly the scope for solar hydrogen power plants along Indian coastline.