Energy Technology 2012: Carbon Dioxide Management and Other Technologies

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Energy Technology 2012: Carbon Dioxide Management and Other Technologies

Proceedings of symposia sponsored by the Energy Committee of

the Extraction and Processing Division and the Light Metals Division of

TMS (The Minerals, Metals & Materials Society)

Held during the TMS 2012 Annual Meeting & Exhibition

Orlando, Florida, USA March 11-15,2012

Edited by

Maria D. Salazar-Villalpando Neale R Neelameggham

Donna Post Guillen Soobhankar Pati

Gregory K. Krumdick

WILEY TMS A John Wiley & Sons, Inc., Publication

Copyright © 2012 by The Minerals, Metals, & Materials Society. All rights reserved.

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TABLE OF CONTENTS Energy Technology 2012

Preface xiii Editors xvii

Energy Technologies and Carbon Dioxide Management

CQ2 Management and Utilization

Solar Activated Photocatalytic Conversion of C02 and Water to Fuels by Ti02-Based Nanocomposites 5

Q. Zhang, L. Liu, and Y. Li

Photocatalytic Efficacy of 1-Dimensional Nanocomposite Electrode 9 J. Lee, B. Ding, J. Noh, and K. Hong

Reduction of Energy Consumption and GHGs Emission in Investment Casting Process by Application of a New Casting Method 15

X. Dai, M. Jolly, and B. Zeng

Bauxite Residue Neutralization and Carbon Sequestration from Flue Gas 23 L. Alves Venancio, E. Negräo Macedo, J. Antonio Silva Souza, andF. Aracati Botelho

50% Reduction of Energy and C02 Emission in Metallurgical Furnaces by Burners 31

M. Potesser, D. Spoljaric, B. Holleis, and M. Demuth

C02 Removal from Industrial Off-Gas Streams by Fluidized Bed Carbonation 39

K. Pericleous, M. Molaei, and M. Patel

A Hydro-Mechanical Model and Analytical Solutions for Geomechanical Modeling of Carbon Dioxide Geological Sequestration 47

Z Xu, Y. Fang, T. Scheibe, and A. Bonneville

v

Energy Technologies Energy Opportunities in the Aluminum Processing Industry 57

C. Belt

An Alternative Lower Temperature Route For The Recovery of Cobalt From Slag 65

A. Jha, and Y. Hara

High Thermal Energy Storage Density LiNOj-NaNOj-KNOj-KNOj Quaternary Molten Salts for Parabolic Trough Solar Power Generation 73

T. Wang, D. Mantha, and R. Reddy

Global Primary Aluminium Industry 2010 Life Cycle Inventory 85 C. Bayliss, M. Bertram, K. Buxmann, B. de Gel as, S. Jones, and L. Wu

Analysis of Combustion Efficiency Using Laser-Induced Fluorescence Measurements of OH-Radicals 93

M. Schnitzler, R. Boiling, andH. Pfeifer

A Solid State Thermoelectric Power Generator Prototype Designed to Recover Radiant Waste Heat 101

M. Takla, O. Burheim, L. Kolbeinsen, andS. Kjelstrup

Study on Smelting Reduction of Coal-Containing Pellets of V-Ti Bearing Beach Placers by Combined Rotary Hearth Furnace and Direct Current Arc Furnace 109

H. Lu, J. Xu, and Q. Li

A Novel Method Combined lonothermal Synthesis and Microwave Energies for Rapid Production of ZIFS 117

L. Yang, H. Lu, andS. Zhou

The Relationship between Energy Consumption and COz Emissions in Iron and Steel Making 125

H. Bai, X. Lu, H. Li, L. Zhao, X. Liu, N. Li, W. Wei, and D. Cang

Development and Application of Shaft Kiln in China 133 L. Guo, M. Xian, and L. Dong

Preparation of Biodiesel by Transesterification of Canola Oil Using Solid Base Catalyst KOH/?-Al203 141

S. Sadrameli, and M. Omraei

VI

Waste Heat Recovery Effect of Materials on the Autoignition of Cyclopentane 151

D. Guillen

Low Grade Waste Heat Driven Desalination and S02 Scrubbing 159 S. Garimella, D. Ziegler, andJ. Klausner

Waste Heat Integration Potential Assessment through Exergy Analysis in an Aluminum Production Facility 165

C. Nowicki, L. Gosselin, andC. Duchesne

Sustainability, Energy Efficiency and C02 Elimination in Concentrate Drying 173

J. Talja, S. Chen, and H. Mansikkaviita

Development of Heat Recovery System from Steelmaking Slag 181 Y. Ta, H. Tobo, Y. Hagio, and M. Kuwayama

Dry Granulation of Molten Blast Furnace Slag and Heat Recovery from Obtained Particles 187

Y. Qin, X. Lv, C. Bai, and G. Qiu

The Environment Load Assessment of Iron and Steel Producing BF-BOF and EAF Route Process 195

H. Li, S. Tao, H. Bai, and D. Cang

Aluminum Smelter Waste Heat Recovery Plant (Heat Exchangers Fouling and Corrosion-A Detailed Investigation) 203

H. Fanisalek, M. Bashiri, and R. Kamali

Battery Recycling

Session I Economic and Environmental Trade-Offs for Li-Based Battery Recycling 219

G. Gaustad, M. Ganter, X. Wang, C. Bailey, C. Babbitt, and B. Landi

Battery Recycling by Hydrometallurgy: Evaluation of Simultaneous Treatment of Several Cell Systems 227

C. Nogueira, and F. Margarido

Vll

The Use of Liquid-Liquid Extraction and Electroplating to Metals Recovery from Spent Batteries 235

K. Provazi, D. Espinosa, andJ. Tenorio

Magnetic Materials for Energy Applications II

Permanent Magnets for Energy Applications

Search for New Rare Earth Based Permanent Magnetic Materials 247 B. Jensen, K. Dennis, and R. McCallum

Magnetocaloric and Magnetostrictive Materials

Effect of W Substitution on the Magnetostrictive Behavior of [001] Fe-Ga Alloy Single Crystal 257

C. Ren, B. Saha, M. Ramanathan, and S. Guruswamy

Power Conversion and Microstructural Effects

Nanocomposite Alloy Design for High Frequency Power Conversion Applications 267

S. Shen, P. Ohodnicki, S. Kernion, A. Leary, V. Keylin, J. Huth, and M. McHenry

Magnetic Properties of Strontium Ferrite Prepared Using Submicron-Sized SrFe]2.xAlxO]9 Powders 275

V. Menushenkov, V. Shubakov, and S, Ketov

Influence of Magnetization on the Hydrogen Embrittlement Behavior in AISI 4340 Steel 281

M. Ramanathan, B. Saha, C. Ren, S. Guruswamy, and M. McCarter

The Effect of Dynamic Electropulsing on Mechanical and Microstructural Properties of Cold Rolled Fe-6.5%Si Alloy Sheet 289

Y. Liang, F. Ye, H. Zhou, F. Wang, G. Tang, andJ. Lin

vin

Materials in Clean Power Systems VII: Clean Coal-, Hydrogen Based-Technologies, and Fuel Cells

Fuel Cells

Study of Microstructure and Electrical Conductivity on (Ce09Nd0 Ι)Ι-ΧΜΧ02-Δ Electrolytes for Intermediate-Temperature Solid Oxide Fuel Cells 301

F. Menga, Y. Xiab, D. Zhouc, N. Trubakia, X. Liub, andJ. Mengb

Transition Metal Doping of Manganese Cobalt Spinel Oxides for Coating SOFC Interconnects 305

J. Fergus, Y. Liu, J. Gcmley, D. Nair, W. Tilson, A. Dekich, D. Kumar, Y. Liu, J. Ganley, W. Tilson, A. Dekich, andJ. Fergus

Materials for Hydrogen Production, Separation, and Storage

Free Form Fabrication of Catalytic Substrates 315 T. Salisbury, J. Downey, W. Gleason, S. Davis, G. Pinson, R. Christianson, M. Berlin, R. James, E. Rosenberg, K. Gleason, R. Hiebert, andJ. McCloskey

Improved Palladium Coatings for Hydrogen Purification Membranes 323 S. Davis, J. Downey, W. Gleason, T. Salisbury, G. Pinson, R. Christianson, M. Berlin, R. James, E. Rosenberg, K. Gleason, R. Hiebert, andJ. McCloskey

Raman Spectroscopy of Ammonia Borane at Low Temperature and High Pressure 331

S. Najiba, J. Chen, V. Drozd, A. Durygin, and Y. Sun

IX

Mechanical Performance of Materials for Current and Advanced Nuclear Reactors

Mechanical Behavior of Reactor Materials

Fracture Toughness of 9Cr-l MoV and Thermally Aged Alloy 617 for Advanced Reactor Applications 343

R. Nanstad, M. Sokolov, andX. Chen

Characterization and Modeling of Microstructural Evolution in Nuclear Materials

Elemental Solubility Tendency for the Phases of Uranium by Classical Models Used to Predict Alloy Behavior 359

V. Blackwood, T. Koenig, J. Porter, D. Olson, B. Mishra, R. Mariani, and D. Porter

Irradiation and Testing of Fuels and Cladding Materials

Nanoindentation and TEM Characterization of Ion Irridiated 316L Stainless Steels 373

K. Hattar, T. Buchheit, P. Kotula, A. McGinnis, and L. Brewer

Processing to Control Morphology and Texture in Magnetic Materials

Processing to Enhance Performance in Rare Earth Permanent Magnets

Cluster Synthesis, Direct Ordering and Alignment of Rare-Earth Transition-Metal Nanomagnets 385

B. Balamurugan, R. Skomski, and D. Le Roy

x

Role of Magnetic Fields and Texturing to Improved Magnetic Materials

Nanostructuring and Texturing for Improved Magnetic Materials 393 D. Sellmyer, Y. Liu, and T. George

Author Index 403

Subject Index 407

Role of Magnetic Fields and Texturing to Improved Magnetic Materials

Nanostructuring and Texturing for Improved Magnetic Materials 393

D. Sellmyer, Y. Liu, and T. George

Author Index 403

Subject Index 407

Preface

This is the fifth symposium organized by the Energy Committee, which was initiated in 2007 - 2008. During the first two years, the symposium on minimizing carbon dioxide emissions by chemical reduction of oxides or physical minimization by other methods was called C02 Reduction Metallurgy. Starting in 2010, the proceedings became Energy Technology - 2010, Energy Technology - 2011, with papers from the symposium on Carbon Dioxide & Other Greenhouse Gas Reduction Metallurgy, and the symposium on Energy Efficiency, Waste Heat Recovery in Metallurgical Processes. It was decided to encompass this in a symposium called "Energy Technologies and Carbon Dioxide Management" starting in 2012. This symposium had the intention to cover technology and processes to improve industrial energy efficiency, reduction in C02 and other greenhouse gases, and alternative energy sources. The aim of this symposium was to pave the way to accomplish an efficient use of energy and manage CO,. It is intended to address the need for sustainable technologies in extractive metallurgy, materials processing and manufacturing industries with reduced energy consumption and C02 emission.

A special session on solar and electrochemical C02 conversion and utilization technologies for fuels synthesis was included, such as (but not limited) photo-electrochemical, photocatalytic, electrochemical and solar thermochemical methods. Industrial energy efficiency technologies and processes can include improved extractive processes along with technologies such as waste heat recovery. The symposium was also open to contributions from all areas of non-nuclear and non-traditional energy sources, including renewable energy - solar, wind, biomass, etc. A strong emphasis was given to the contributions focusing on reduction of atmospheric C02 and conversion of CO, into high value products. Moreover, initial attention was given to the "Cap and Trade" legislation progresses towards possible enactment and/or U.S. EPA using existing authority of "Clean A ir Act" to regulate carbon dioxide as pollutants, it is critical to study and devise implementable technologies, such as establish carbon footprints and life cycle analysis; develop carbon footprint mitigation portfolio & suggest implementation strategies; develop carbon credits and offsets for mandatory & voluntary markets, etc.

The Energy Technologies and Carbon Dioxide Management symposium included topics (but not limited) such as: C02 and Other Greenhouse Gas Reduction Metallurgy, Alternative Renewable Energy Resources for Metals and Materials Production, Solar and electrochemical C02 conversion and Energy Management Waste Heat Recovery and Other Industrial Energy Efficient Technologies.

These present proceedings on Energy Technology 2012 decided to include papers from some of the other stand alone symposiums on Energy related topics from other Divisions of TMS other than from the Energy Committee which is part of EPD and LMD.

X l l l

These proceedings cover several symposiums, Energy Technologies and Carbon Dioxide Management, Battery Recycling, Magnetic Materials for Energy Applications II, Materials in Clean Power Systems VII: Clean Coal-, Hydrogen Based-Technologies, Mechanical Performance of Materials for Current and Advanced Nuclear Reactors and Processing to Control Morphology and Texture in Magnetic Materials.

There are 45 papers among these symposiums - of those close to 30 papers belong to Energy Technologies and Carbon Dioxide Management symposium forming three sessions during the 2012 TMS Annual Meeting.

We wish to acknowledge efforts by Energy committee Chair Cindy Belt and Vice Chair Jarek Drelich in enhancing the Proceedings of Energy Technology 2012.

We thank the efforts by the rest of the non-editor-co-organizers Subodh Das, Ramana Reddy, Animesh Jha, Mark Jolly and Lakshmanan Vaikuntam from the Energy Technologies and Carbon Dioxide Management Symposium. We also acknowledge the organizers of the rest of the symposiums, papers from which were added to the proceedings (special thanks to Gregory K. Krumdick from editing the papers from his symposium):

Battery Recycling

Gregory K. Krumdick

Magnetic Materials for Energy Applications II

Raju V. Ramanujan, Nanyang Technological University Francis Johnson, GE Global Research S. Guruswamy, Univ. of Utah J. Liu, Electron Energy Corporation

Materials in Clean Power Systems VII: Clean Coal-, Hydrogen Based-Technologies

Xingbo Liu, West Virginia University Teruhisa Horita, National Institute of Advanced Industrial Science and Technology Jeffrey Hawk, National Energy Technology Lab Jeffrey Fergus, Auburn University

Mechanical Performance of Materials for Current and Advanced Nuclear Reactors

Nicholas Barbosa, National Institute of Standards & Tech Greg Oberson, United States Nuclear Regulatory Commission Matthew Kerr, United States Nuclear Regulatory Commission Elaine West, Knolls Atomic Power Laboratory Stuart Maloy, Los Alamos National Laboratory Osman Anderoglu, LANL

xiv

Processing to Control Morphology and Texture in Magnetic Materials

Matthew Kramer, Iowa State University Mike McHenry, Carnegie Mellon University David Laughlin, Carnegie Mellon University Jinfang Liu, Electron Energy Corporation Bill Soffa, University of Virginia

Editors: Maria D. Salazar-Villalpando, Neale R Neeiameggham, Donna Post Guillen, Soobhankar Pati and Gregory K. Krumdick

xv

Processing to Control Morphology and Texture in Magnetic Materials

Matthew Kramer, Iowa State University Mike McHenry, Carnegie Mellon University David Laughlin, Carnegie Mellon University Jinfang Liu, Electron Energy Corporation Bill Soffa, University of Virginia

Editors: Maria D. Salazar-Villalpando, Neale R Neeiameggham, Donna Post Guillen, Soobhankar Pati and Gregory K. Krumdick

xv

Editors

Maria D. Salazar-Villalpando is a research leader for the photo-electro-catalysis group at the Department of Energy's National Energy Technology Laboratory (NETL) where she has been responsible for conceiving and developing highly innovative projects in C02 utilization. She has also carried out research in Hydrogen and syn-gas production by heterogeneous methods at NETL. She has over 15 years of expertise over a wide cross section of energy and environmental technologies, such as catalyst development, photo and electrochemical processes, PEM and SOFC fuel cells. She has worked in projects that monitored and evaluated pollutants from PEMEX's petrochemicals and refineries. She has received training in several countries, including Mexico, Sweden, Canada, and the USA. She has worked in three research institutes, the Mexican Petroleum Institute, the Electrical Research Institute, and the NETL. She did her post-doc at the West Virginia University, where later became an assistant professor. She has been the recipient of several honors and awards, receiving the 2009 Hispanic Employee of the year Honorable Mention by the Pittsburgh Federal Executive Board Hispanic Employment Program Committee and the Fulbright Scholarship award in 1995 to pursue a Ph.D. in Chemical Engineering at the Illinois Institute of Technology. She has published scientific publications in peer reviewed journals and belongs to the editorial board of the International Journal of Hydrogen Energy. She has served as chair, co-chair and symposium co-organizer for the TMS and ECS Societies in C02 reduction or utilization for several years. As a member of the TMS, She has co-organized two symposiums in C02 reduction Metallurgy. She is the lead organizer and lead editor of the Energy Technology 2012 Symposium and proceedings, respectively. She is also member of the TMS Energy Committee. Dr. Salazar holds a doctorate in Chemical Engineering from the Illinois Institute of Technology.

xvn

Neale R. Neelameggham is 'Guru' at IND LLC, involved in Technology marketing and consulting in the field of light metals and associated chemicals [boron, magnesium, titanium, lithium and alkali metals], rare earth elements, battery and energy technologies, etc. He has over 38 years of expertise in magnesium production technology from the Great Salt Lake brine in Utah, involved in Process Development of its startup company NL magnesium through the presently known US Magnesium LLC, and was its Technical Development Scientist from where he retired. Dr. Neelameggham's expertise includes all aspects of the magnesium process, from solar ponds through the cast house including solvent extraction, spray drying, molten salt chlorination, electrolytic cell and furnace designs, lithium ion battery chemicals and by-product chemical processing. In addition, he has an in-depth and detailed knowledge of alloy development as well as all competing technologies of magnesium production, both electrolytic and thermal processes worldwide. Dr. Neelameggham holds 13 patents and a pending patent on Boron Production, and has several technical papers to his credit.

As a member of TMS, AlChE, and a former member of American Ceramics Society he is well versed in energy engineering, bio-fuels, rare-earth minerals and metal processing and related processes. Dr. Neelameggham has served in the Magnesium Committee of LMD since its inception in 2000, chaired it in 2005, and has been a co-organizer of the Magnesium Symposium since 2004. In 2007 he was made a Permanent Co-organizer for the Magnesium Symposium. He has been a member of the Reactive Metals Committee, Recycling Committee and Programming Committee Representative of LMD. In 2008, LMD and EPD created the Energy Committee following the symposium on C02 Reduction Metallurgy Symposium initiated by him. Dr. Neelameggham was selected as the inaugural Chair for the Energy Committee with a two-year term. He was a member of LMD council. He received the LMD Distingusished Service Award in 2010. He has been a co-editor of the Energy Technology symposium. Dr. Neelameggham holds a doctorate in extractive metallurgy from the University of Utah.

xvin

Donna Post Guillen earned a B.S. in Mechanical Engineering from Rutgers University, an M.S. in Aeronautics from California Institute of Technology, and a Ph.D. in Engineering and Applied Science from Idaho State University. She is currently a Group Lead for Process Modeling at the Idaho National Laboratory (INL), has served as an Adjunct Professor at Idaho State University and Utah State University, is a registered Professional Engineer with over 25 years of experience, and has authored more than 65 technical publications, including two books. She is the lead inventor on two patent applications for a new metal matrix composite material developed and fabricated at INL. As Principal Investigator for several multi-million dollar projects, she performs analyses, directs experiments, and provides leadership to multidisciplinary technical teams involving mechanical, chemical, nuclear and materials engineering expertise. The focus of her research is multiphase computational fluid dynamics and thermal hydraulics for sustainable energy technologies.

Soobhankar Pati is a Research Engineer at Metal Oxygen Separation Technology Inc. (MOxST), Natick, MA, which is commercializing a revolutionary process for electrolytic production of metals directly from their oxides. In addition, Soobhankar is a Visiting Scientist at Boston University in the Department of Materials Science and Engineering, where he received a Ph.D. in 2010. At Boston University, his contributions led to breakthroughs which reduced the cost of pure oxygen production in this direct oxide electrolysis process, made gas handling in the process much simpler and more robust, and facilitated scale-up of the process from a few grams to kilogram scale. As part of his graduate research he developed a new technology for using the energy in industrial and municipal waste to directly make hydrogen gas at high efficiency. His research work at Boston University won various clean energy awards. He is currently a member of TMS and actively takes part regularly in Energy Committee and Magnesium Committee activities.

if

XIX

Gregory K. Krumdick is a principal systems engineer in the Energy Systems Division at Argonne National Laboratory. He earned his MS degree in Bioengineering from the University of Illinois at Chicago, focusing on process control systems. Mr. Krumdick has spent the past 20 years with Argonne, where he has been the principal investigator on numerous industrial process scale-up projects and lead engineer on several pilot plant systems for the Process Technology Research section. Currently, Mr. Krumdick is leading Argonne's battery materials scale-up program and is overseeing the construction of Argonne's new Materials Engineering Facility.

xx

Energy Technology 2012: Carbon Dioxide Management and Other Technologies

Energy Technologies and Carbon Dioxide Management

Organizers:

Maria Salazar-Villalpando Neale R. Neelameggham

Donna P. Guillen Subodh Das

Ramana Reddy Animesh Jha

Soobhankar Pati Mark Jolly

Lakshmanan Vaikuntam

Energy Technology 2012: Carbon Dioxide Management and Other Technologies

Energy Technologies and Carbon Dioxide Management

Organizers:

Maria Salazar-Villalpando Neale R. Neelameggham

Donna P. Guillen Subodh Das

Ramana Reddy Animesh Jha

Soobhankar Pati Mark Jolly

Lakshmanan Vaikuntam

Energy Technology 2012: Carbon Dioxide Management and Other Technologies

C02 Management and Utilization

Session Chairs: Mahesh Jha

Maria Salazar-Villalpando Animesh Jha

Soobhankar Pati

Energy Technology 2012: Carbon Dioxide Management and Other Technologies

C02 Management and Utilization

Session Chairs: Mahesh Jha

Maria Salazar-Villalpando Animesh Jha

Soobhankar Pati

Energy Technology 2012: Carbon Dioxide Management and Other Technologies Edited by: Maria D. Salazar-Villalpando, Neale R Neelameggham, Donna Post Guillen, Soobhankar Pali, and Gregory K. Krumdick

TMS (The Minerals, Metals & Materials Society), 2012

Solar Activated Photocatalytic Conversion of C 0 2 and Water to Fuels by

Ti02-Based Nanocomposites

Qianyi Zhang, Lianjun Liu, Ying Li*

University of Wisconsin-Milwaukee 3200 N Cramer Street, Milwaukee, Wisconsin

* Corresponding author: liying;«)uwtri.edu

Keywords: Photocatalysis; CO2 Conversion; T1O2; Doping; Nanomaterials

Abstract Photocatalytic reduction of CO2 by H2O for production of Cl fuels (CO and CH4) was studied using copper and iodine co-modified T1O2 (Cu-I/Ti02) nanocomposites, with copper deposited on the surface and iodine doped in the lattice. The nanocomposites were prepared via a combined hydrothermal and wet impregnation process. All 1-doped samples demonstrated visible light activity. Under UV-vis irradiation, co-modification of Cu and I significantly increased T1O2 photoactivity compared with bare T1O2 or those modified with only one species.

Introduction The photoreduction of CO2 into fuels on photocatalysts such as T1O2 has been regarded as an important approach to solve both energy shortage and globe warming problems [1]. However, the wide band gap and fast recombination of photoinduced hole (h+) and electrons (e') limited the application of T1O2 in CO2 photoreduction reaction. Extensive research has been conducted to improve the photocatalytic ability of T1O2 by depositing or doping foreign ions that can enhance charge transfer and/or creates intra-band-gap states to induce visible light absorption at the sub-band-gap energy. Compared with mono-doping, co-doping of metal/nonmetal species has been reported to have higher photocatalytic activity for T1O2 [1-3]. Our previous studies showed that Cu deposited on T1O2 [4] or iodine doped in T1O2 [5] significantly enhanced the catalytic efficiency for CO2 photoreduction and increased the response to visible light. We hypothesize that there could be a synergetic effect if T1O2 is co-modified by both Cu and I species resulting in further improvement in CO2 reduction efficiency. In this work, we synthesized and characterized CU-I/T1O2 samples and investigated their activity toward CO2 reduction under visible and UV-vis illumination, respectively.

Experimental Methods Materials Titanium tetra-isopropoxide (TTIP, 98%) and isopropanol (CsHsO, 99.8%) were purchased from Acros Organic. lodic acid (H103,99.8%) and Copper Chloride (C11CI2, 99.9%) were purchased from Alfa Aesar. All other chemicals were analytical grade and used without further treatment.

Preparation I-doped T1O2 was first synthesized following a hydrothermal method using TTIP and HIO3 as the precursors, as reported in our previous work [5]. The iodine concentration was fixed at 10 wt% in this work. CU-I/T1O2 sample was then prepared through a wet impregnation method by using as-prepared I-T1O2 sample and CuCh as the Cu precursor. Cu concentration varied from 0.1 to 1 wt%. For comparison, pure T1O2 and CU-T1O2 were prepared following the same

5

procedure. All samples were grinded and sieved by a 45 μπι stainless steel sieve before characterization and photoreduction tests.

Characterization The crystalline phase was examined by X-ray diffraction (XRD) and the crystalline size was estimated by Scherrer equation. In addition, UV-vis diffuse reflectance spectra were measured at room temperature by a UV-vis spectrometer, where the bandgap energy can be calculated.

Photoreduction experiment The experiments of photocatalytic reduction of C0 2 were carried out in a reactor that has stainless steel walls and a quartz window. The catalyst (100 mg) was spread on a glass fiber filter at the bottom of the reactor. Λ 450 W Xe lamp was used as the light source for UV-vis irradiation and a long-pass UV filter was applied when only visible light (λ > 400 nm) was needed. A mixture of CO2 and water vapor was introduced to the reactor and the gas samples from the reactor during the photoreaction process were taken by a syringe and measured by a gas Chromatograph with a thermal conductivity detector (TCD) and flame ionization detector (FID).

Results and Discussion Characterization of Cu-l/TiO? The XRD results indicate that all TiC>2-containing samples have mixture phases of anatase and brookite, which agrees with those reported in our previous study [5]. Tablel summarized the phase content, crystalline size and band gap of these Ti02-based catalysts. Compared with bare T1O2, the addition of Cu resulted in not only an increased phase content of brookite but also a larger crystalline size of anatase. Whereas, the doping of iodine seemed to slightly induce the transformation of anatase to brookite and decreased the size of anatase. Moreover, the co-presence of Cu and I further decreased the crystalline size of brookite. The band gap of the T1O2 was narrowed due to the iodine doping, which is line with our previous results [5]. But the addition of Cu species did not have apparent effect on the band gap, indicating Cu is deposited on the Ti02 surface rather than in the lattice.

Photocatalytic Activity Carbon monoxide (CO) was the major product observed in our CO2 photoreduction process. As shown in Figure la, under visible light pure Ti02 and Cu/Ti02 had no activity, whereas I/Ti02 samples demonstrated good photocatalytic activity for CO2 reduction to CO. Cu-I/Ti02 samples, however, did not have a better activity than 1/Ti02 samples. Figure 2b shows that under UV-vis light illumination, all Ti02-based samples demonstrated activity for CO2 reduction to CO and Cu-I/Ti02 samples have the highest activity than bare T1O2, Cu/Ti02, or I/T1O2, indicating a synergetic effect ofCu and 1 species. For the Cu-1/Ti02 samples, 0.1% Cu shows the highest activity under UV-vis irradiation but 1% Cu under visible light. It is reported that excessive Cu species may form recombination centers of photo-induced electrons and holes [4]. Because UV-vis irradiation generates much more photo-induced charges than visible light does, the rate of charge recombination may be higher under UV-vis. Hence, it is reasonable that the optimum Cu concentration observed under visible light (1%) could have already performed as recombination centers under UV-vis irradiation, which explains that the optimum Cu concentration is lower (0.1%) under UV-vis irradiation.

6

Table 1. Phase content, crystalline size, and band gap of the prepared Ti02-basedphotocatalysts. (A - anatase; B = brookite)

Sample

Ti02

10%l/TiO2

l%Cu/Ti02

l%Cu-10%l/TiO2

Phase Content (%)

A

70 67

54

58

B

30

33

46

42

Crystalline Size (nm)

A

8.9

5.6 9.6

6.9

B

4.8

5.3

4.1

3.7

Band Cap (eV)

3.10 2.88

3.04

2.87

8 -i 1 14

0 50 100 150 200

Figure 1. Time dependence on the yield of CO for various catalysts under visible light (a) and UV-vis (b) irradiation

Summary Cu and I co-modified T1O2 nanocomposites were prepared and tested for photocatalytic CO2 reduction with water. Cu and 1 modification influenced the crystal structure and crystalline size of the catalyst. CO was found to be the primary reaction product. Visible light activity was enhanced due to iodine doping. A synergetic effect of Cu and 1 was observed for CO2 photoreduction under UV-vis irradiation.

Reference [1] Anpo, M et al., "Photocatalytic Reduction of CO2 With H2O on Various Titanium-Oxide Catalysts", J Electroanal Chem, 396 (1-2), 1995, 21-26.

[2] Zhang, SS et al., "Electrodeposition Preparation of Ag Loaded N-Doped T1O2 Nanotube Arrays With Enhanced Visible Light Photocatalytic Performance", Catal Commun, 12 (8), 2011, 689-693.

[3] Jia, LC et al.,"Theoretical Study on the Electronic and Optical Properties of (N, Fe)-Codoped Anatase Ti02 Photocatalyst", J Alloy Compd, 509 (20), 2011, 6067-6071.

[4] Li,Y et al.,"Photocatalytic Reduction of C02 With H2O on Mesoporous Silica Supported Cu/Ti02 Catalysts", Appl Catal B-Environ, 100 (1 -2), 2010, 386-392.

[5] Zhang, QY et al.,"Visible Light Responsive Iodine-Doped T1O2 for Photocatalytic Reduction of C0 2 to Fuels", Appl Catal A-Gen, 400 (1-2), 2011, 195-202.

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Table 1. Phase content, crystalline size, and band gap of the prepared Ti02-basedphotocatalysts. (A - anatase; B = brookite)

Sample

Ti02

10%l/TiO2

l%Cu/Ti02

l%Cu-10%l/TiO2

Phase Content (%)

A

70 67

54

58

B

30

33

46

42

Crystalline Size (nm)

A

8.9

5.6 9.6

6.9

B

4.8

5.3

4.1

3.7

Band Cap (eV)

3.10 2.88

3.04

2.87

8 -i 1 14

0 50 100 150 200

Figure 1. Time dependence on the yield of CO for various catalysts under visible light (a) and UV-vis (b) irradiation

Summary Cu and I co-modified T1O2 nanocomposites were prepared and tested for photocatalytic CO2 reduction with water. Cu and 1 modification influenced the crystal structure and crystalline size of the catalyst. CO was found to be the primary reaction product. Visible light activity was enhanced due to iodine doping. A synergetic effect of Cu and 1 was observed for CO2 photoreduction under UV-vis irradiation.

Reference [1] Anpo, M et al., "Photocatalytic Reduction of CO2 With H2O on Various Titanium-Oxide Catalysts", J Electroanal Chem, 396 (1-2), 1995, 21-26.

[2] Zhang, SS et al., "Electrodeposition Preparation of Ag Loaded N-Doped T1O2 Nanotube Arrays With Enhanced Visible Light Photocatalytic Performance", Catal Commun, 12 (8), 2011, 689-693.

[3] Jia, LC et al.,"Theoretical Study on the Electronic and Optical Properties of (N, Fe)-Codoped Anatase Ti02 Photocatalyst", J Alloy Compd, 509 (20), 2011, 6067-6071.

[4] Li,Y et al.,"Photocatalytic Reduction of C02 With H2O on Mesoporous Silica Supported Cu/Ti02 Catalysts", Appl Catal B-Environ, 100 (1 -2), 2010, 386-392.

[5] Zhang, QY et al.,"Visible Light Responsive Iodine-Doped T1O2 for Photocatalytic Reduction of C0 2 to Fuels", Appl Catal A-Gen, 400 (1-2), 2011, 195-202.

7