Quantum size effect of transition metal oxide catalysts

过渡金属氧化物催化剂的量子尺寸效应

• 批准号: 08405052
• 负责人: YOSHIDA Satohiro
• 金额: $ 25.6万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08405052/
• 关键词: supported catalyst; quantum size effect; binary metal oxide; solid solution; XAFS; characterization; photocatalyst; phtocatalyst; キャラクラリゼーション; 量子効果; 微粒子; 遷移金属酸化物; 担体; NOx還元; メタセシス; 金属酸化物; 触媒; 構造解析; ラマン分光法; キャラクタリゼーション

Systematic investigation of 'quantum size effect' was carried out for the micro particles of oxides of magnesium, titanium, vanadium, manganese, iron, cobalt, copper, garium, niobium, molybdenum, lanthanides, rhodium and tungstenum dispersed on various metal oxide supports.1. Characterization of the samples carried out mainly by XAFS led the following structural results. (1) Over the silica support ; magnesium and copper are supported as a micro particle which exhibits quantum size effect, lanthanide is stabilized as a two-dimensional metal oxide, and titanium, vanadium, niobium, garium, and tungstenum are dispersed atomically, and atomically dispersed sample exhibits photoactivity. (2) Over alumina and magnesia support ; every metal cations are dispersed atomically and binary metal oxides are formed at a high loading. (3) Over titania support ; metal cations are stabilized atomically at a low loading. Metallic elements are converted to metal particle sizing in ca. 100 *. (4) zirconium and iron oxides form a solid solution.2. The catalysts above are able to be applied to the reactions below. (1) Selective photooxidation of light alkanes over silica-supported vanadium oxide. (2) Acid-catalyzed reaction over silica-supported lanthanide oxides. (3) Selective oxidation of olefins over silica-supported titanium oxide. (4) oxidation of methane over silica-supported tungstenum oxide. (5) Selective reduction of NOx over titanium supported copper. (6) Photoreduction of carbon dioxide over titania-supported rhodium. (7) Olefin metathesis over Mg-Mo binary metal oxide. (8) Epoxidation of olefins over supported magnesium oxide.

系统地研究了分散在各种金属氧化物载体上的镁、钛、钒、锰、铁、钴、铜、镓、铌、钼、镧系元素、铑和钨的氧化物微粒的“量子尺寸效应”.主要通过XAFS进行的样品表征导致以下结构结果。(1)在二氧化硅载体上;镁和铜被负载为表现出量子尺寸效应的微粒，镧系元素被稳定为二维金属氧化物，钛、钒、铌、镓和钨原子级分散，原子级分散的样品表现出光活性。(2)在氧化铝和氧化镁载体上，每种金属阳离子以原子形式分散，并在高负载下形成二元金属氧化物。(3)在二氧化钛载体上，金属阳离子在低负载下原子稳定。金属元素被转化为金属颗粒尺寸在ca。100 *。(4)锆和铁的氧化物形成固溶体。上述催化剂能够应用于以下反应。(1)二氧化硅负载钒氧化物上低碳烷烃的选择性光氧化。(2)二氧化硅负载镧系氧化物上的酸催化反应。(3)烯烃在二氧化硅负载的氧化钛上的选择性氧化。(4)甲烷在二氧化硅负载的氧化钨上的氧化。(5)在钛载铜上选择性还原NOx。(6)二氧化碳在二氧化钛负载铑上的光还原。(7)Mg-Mo二元金属氧化物上的烯烃复分解反应。(8)负载型氧化镁催化烯烃环氧化反应。

项目成果

Sakae Takenaka: "Structures of Molybdenum Species in Silica-Supported Molybdenum Oxide and Alkali-lon-Modified Silica-Supported Molybdenum Oxide" Journal of Physcal Chemistry B. 102. 2960-2969 (1998)

Sakae Takenaka：“二氧化硅负载的氧化钼和碱基改性二氧化硅负载的氧化钼中钼物质的结构”物理化学杂志 B. 102. 2960-2969 (1998)

Sakae Takenaka: "Structure of Active Species in Alkali-Ion-Modified Silica-Supported Vanadium Oxide" Journal of Physcal Chemistry B. 101. 9035-9045 (1997)

Sakae Takenaka：“碱离子改性二氧化硅负载的氧化钒中活性物质的结构”物理化学杂志 B. 101. 9035-9045 (1997)

Yasuhiro Iwasawa: "X-Ray Absorption Fine Structure for Catalysts and Surfaces" World Scienfic. 304-325 (1996)

Yasuhiro Iwasawa：“催化剂和表面的 X 射线吸收精细结构”世界科学。

Tsunehiro Tanaka: "Application of XANES Spectra to Supported Catalysts" Japan Journal of Applied Physics. (印刷中).

Tsunehiro Tanaka：“XANES 光谱在负载型催化剂中的应用”，日本应用物理学杂志（正在出版）。

Hirofumi Aritani: "Reduction of NO over TiO_2-supported Cu catalysts" Journal of Chemical Societry, Faraday Transactions. 92. 2625-2630 (1996)

Hirofumi Aritani：“通过 TiO_2 支撑的 Cu 催化剂还原 NO”，化学会杂志，法拉第会刊。