Nano-structured Complex Metal Oxide Catalysts Catalysis Research - PowerPoint PPT Presentation

Nano-structured Complex Metal Oxide Catalysts Catalysis Research Center, Hokkaido University Wataru Ueda April 20, 2009

Hokkaido University Catalysis Research Center The national collaborating institution in the field of catalysis in Japan

History Sapporo city Hokkaido University Campus CRC Catalysis Research Center (CRC) originated from the Institute of Catalysis which was founded in 1943 in Hokkaido University for fundamental studies on catalysis, and started as a national collaborating institution in 1988, followed by scale-up reorganization in 1998 and by a organization renewal in 2007 for playing a leading role in catalysis studies and a bridging role among interdisciplinary scientific researches.

Multifunctional activity Fundamental CRC researches supported by government, JSPS, JST, etc. Only one research, Challenging research, CRC New field research Collaborative research projects organized 7 professors by CRC with researchers in Japan 7 associate professors 6 assistant professors Research projects with companies, NEDO, etc. 29 research fellows Research networking 5 visiting professors Catalysis Summit 19 collaborative Various scientific open facilities researchers 58 students International collaborations 13 tentative stuffs International symposium 8 technical stuffs Joint laboratories in China International research exchange program 20 Administrative stuffs Domestic activity for catalysis community 172 Total Various scientific symposium, seminar Educational activities Global COE program Students from various faculties of Hokkaido Univ. Educational program for researchers

CRC Research Structure: Sections and Clusters Researchers Integrated Research Section outside CRC Research Cluster for Networking of Researchers in Catalytic Science Research Cluster of Asymmetric Induction of Non-Centrochirality as Novel Media Research Cluster of Well-Defined Surface Material Synthesis in Controlled Reaction Field Research Cluster of Functionalized Crystals Research Cluster of Energy Conversion Field Research Cluster for Biomass Conversion Research Cluster of Bio-Interface Extensive Research Section Section of Surface Structure Chemistry Target- -Oriented Oriented Target Section of Interfacial Spectrochemistry Research Research Section of Catalytic Reaction Chemistry Assembly Assembly Section of Catalytic Materials Chemistry Section of Catalytic Transformation Section of Catalytic Assemblies Fundamental Research Fundamental Research Section of Molecular Division Division Catalysis Chemistry Technical Division

Recent topics Collaboration between Catalysis and Nature for the Realization of Sustainable Development Nature step (Photosynthesis) Artificial Catalytic step Supported Pt or Ru catalysts can A new photocatalytic water convert cellulose into sugar alcohols splitting system was developed to such as sorbitol and mannitol by an mimic natural photosynthesis, in environmentally benign process. The which two photoexcitation steps process provides new opportunities were combined. The process for the utilization of abundant and allows visible light to be utilized inexpensive cellulose as a chemical efficiently and a wide spectrum of feedstock. visible light. Fukuoka, Angew. Chem. Int. Ed ., Abe, Chem. Phys. Lett . 2008 2006

Nano-structured Complex Metal Oxide Catalysts Catalysis Research Center, Hokkaido University Wataru Ueda April 20, 2009

Research Framework Thermoelectro material New type fuel Layered Layered cell Polyoxom etalates Polyoxom etalates Nano Nano- - sheet sheet Photo Macro-level design catalysts Complex metal Complex metal Nano- Nano - cube, cube, Atomic-level design oxides oxides fiber fiber Acid catalysts Octahedaral m olecular m olecular Octahedaral Nano-level design sieves ( OMS) sieves ( OMS) Oxidation Three - Three - dim entionally dim entionally catalysts Order m aterial ( 3 DOM) Order m aterial ( 3 DOM) Catalytic filter (Oxidative shoot removal)

Multifunctional Complex Metal Oxide Multifunctional Complex Metal Oxide Multicomponent Molecularity Bi-Fe-Mo-O Heteropoly compounds Olefin oxidation H 2 O 2 oxidation Three dimensional Gas-phase oxidation Redox V-P-O Alkane oxidation Zeolite Porous property Titanosilicate H 2 O 2 oxidation

Mo 3 VOx Complex Metal Oxide Crystals Mo 3 VOx Complex Metal Oxide Crystals 1. Crystal formation mechanism 2. Microporocity 3. Catalytic reactions 2- + VO 2+ 2- + VO 2+ MoO 4 MoO 4 CH 3 COOH CH 3 COOH C 2 H 6 C 2 H 6 O 2 , H 2 O O 2 , H 2 O RCH 2 OH RCH 2 OH Structure unit Structure unit O 2 O 2 RCHO RCHO Adsorption of small molecules like Adsorption of small molecules like H 2 O, CO 2 , O 2 , N 2 , CH 4 , and C 2 H 6 H 2 O, CO 2 , O 2 , N 2 , CH 4 , and C 2 H 6 (Octahedra Molecular sieves) (Octahedra Molecular sieves) b b b b a a a a c c c c Unit condensate （ Mo 3 VOx) Unit condensate （ Mo 3 VOx) Cluster(Mo 72 V 30 Ox) Cluster(Mo 72 V 30 Ox) Orthorhombic Trigonal Orthorhombic Trigonal

Catalyst preparation- -Hydrothermal synthesis Hydrothermal synthesis- - Catalyst preparation (NH 4 ) 6 Mo 7 O 24 ・ 4H 2 O (aqueous solution) ＋ VOSO 4 ・ nH 2 O (Mo:V = 4 : 1) Hydrothermal synthesis Hydrothermal synthesis Crystal + in autoclave (Teflon inner tube) in autoclave (Teflon inner tube) Filtration, Amorphous Washing, and Drying at 80 ºC 175 ºC 48 h Purification Aqueous solution Intensity / a.u. Stirring of oxalic acid Orthorhombic Amorphous 0.4 mol /l at 60 ºC pH 0.69 Filtration, Mo 3 VOx Washing, and Drying at 80 ºC 0 10 20 30 40 50 60 2 θ / deg. crystalline Mo 3 VOx

Structure comparison Structure comparison a a a b Trigonal phase Orthorhombic phase Assembly of [Mo 6 O 21 ] 6- , as the structural unit Octahedral coordination Sadakane, Ueda, Angew. Chem. Int. Ed. (2007) chemistry

Effect of calcination calcination on adsorption capacity on adsorption capacity Effect of Desorption rate (a.u.) ： NH 4 + + desorption NH 4 NH 3 TPD at 300 ℃ 0 100 200 300 400 500 600 Temperature ( ℃ ) 12 MoVO-AC 9 V [ml(STP)/g] 6 + type orthorhombic Mo 3 VO x NH 4 3 N 2 adsorption Air calcination 400 ℃ 0 1.0 × 10 -6 1.0 × 10 -4 1.0 × 10 -2 1.0 × 10 -8 1.0 P/P 0 [-]

Adsorption of various small molecules Adsorption of various small molecules 0.03 Kr CO 2 CH 4 H 2 O Pore volume 0.02 C 2 H 6 (cm 3 /g) 0.01 n-C 6 H 14 n-C 4 H 10 0 0.25 0.3 0.35 0.4 0.45 0.5 Kinetic diameter (nm) DA method was used, 0.4 nm 0.39 nm diameter The heptagonal ring 0.0234 cm 3 /g Sadakane, Ueda, Angew. Chem. Int. Ed. (2008)

Nano- -structured Complex Metal Oxide Catalysts structured Complex Metal Oxide Catalysts Nano Summary • Crystal formation mechanism---Cluster unit to solid 2. Microporocity--- New octahedra molecular sieve with redox property 3. Catalytic reactions---High performance and active pore site 2- + VO 2+ 2- + VO 2+ MoO 4 MoO 4 CH 3 COOH CH 3 COOH C 2 H 6 C 2 H 6 O 2 , H 2 O O 2 , H 2 O RCH 2 OH RCH 2 OH Structure unit Structure unit O 2 O 2 RCHO RCHO Adsorption of small molecules like Adsorption of small molecules like H 2 O, CO 2 , O 2 , N 2 , CH 4 , and C 2 H 6 H 2 O, CO 2 , O 2 , N 2 , CH 4 , and C 2 H 6 (Octahedra Molecular sieves) (Octahedra Molecular sieves) b b b b a a a a c c c c Unit condensate （ Mo 3 VOx) Unit condensate （ Mo 3 VOx) Cluster(Mo 72 V 30 Ox) Cluster(Mo 72 V 30 Ox) Orthorhombic Trigonal Orthorhombic Trigonal