Development of Phototalytic Process for Selective Oxidation of Alkansor

Alkansor 选择性氧化光催化工艺的发展

• 批准号: 08555197
• 负责人: YOSHIDA Satohiro
• 金额: $ 4.61万
• 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 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08555197/
• 关键词: alkane oxidation; photocatalysis; reaction process; alkali-ion promotor; silica; vandum oxide; propane; isobutane; アルカン酸化; バナジウム; 酸化チタン; アルカリイオン

The addition of alkali ions to V_2O_5/SiO_2 enhances catalytic activity as well as changes the effective wavelengh ; excited by irradiation with the light lambda>400 nm. The reactivity of the surface species interacting with Rb ions in the photo-oxidation of isobutane has been investigated to clarify the mechanism of photooxidation of alkanes. Acetone and C_4-compounds were formed. The most striking point is the formation of tert-butyl alcohol over the Rb^+-modified catalyst. A tracer study with ^<18>O_2 showed that oxygen atoms incorporated into tert-butyl alcohol were from gaseous oxygen, whereas acetone contained ^<16>O which originated from the lattice oxygen in the catalyst. The quantum chemical calculations of the active species were carried out and we found that the position of the excited positive hole is different between alkali-ion-doped and undoped samples, which corresponds to the difference of excitation energy. The continuous flow reactor was tested for the oxidation system. The conversion was 1.2% and the selectivity to acetone was found to be 70%. The catalyst deactivation could not be seen for 8-hours duration.

V_2O_5/SiO_2中添加碱离子增强了催化活性，同时改变了有效波长；通过用λ>400nm的光照射而激发。研究了异丁烷光氧化中表面物质与 Rb 离子相互作用的反应性，以阐明烷烃的光氧化机理。形成丙酮和C_4-化合物。最引人注目的一点是在 Rb^+ 改性催化剂上形成叔丁醇。用^ 18 O_2 示踪研究表明，叔丁醇中引入的氧原子来自气态氧，而丙酮中含有^ 16 O，其源自催化剂中的晶格氧。对活性物质进行了量子化学计算，发现碱离子掺杂和未掺杂样品中激发正空穴的位置不同，这对应于激发能的差异。对连续流反应器的氧化系统进行了测试。转化率为1.2%并且丙酮的选择性为70%。 8小时内未见催化剂失活。

项目成果

Satohiro Yoshida: "XAFS of Photocatalysts Comprized of Highly Dispersed Metal Oxides on Supports" Hyomen Kagaku. 18. 21-28 (1997)

Satohiro Yoshida：“由高度分散的金属氧化物组成的光催化剂的 XAFS”Hyomen Kagaku。

Satohiro Yoshida: "Ultra Highly Dispersed Titanium Oxide on SiLica : Effect of Precursors on the Structure and Photocatalysis" J.Phys.IV(colloque C_2). 7. 859-861 (1997)

Satohiro Yoshida：“二氧化硅上的超高度分散二氧化钛：前体对结构和光催化的影响”J.Phys.IV（colloque C_2）。

S.Takenaka: "Selective Partial Oxidation of Light Alkanes over Alkali-Ion-Modified Silica-supported Vanadium Oxides Excited with Visibb Light" Catal.Lett.44. 67-74 (1997)

S.Takenaka：“用 Visibb 光激发的碱离子改性二氧化硅支撑的钒氧化物上轻质烷烃的选择性部分氧化”Catal.Lett.44。

Satohiro Yoshida: "Ultra Highly Dispersed Titanium Oxide on Silica : Effect of Precursors on the Struclure and Photocatalysis" J.Phys.IV (colloque C_2). 7. 859-861 (1997)

Satohiro Yoshida：“二氧化硅上的超高度分散二氧化钛：前体对结构和光催化的影响”J.Phys.IV（colloque C_2）。

吉田 郷弘: "高分散担持酸化物触媒のXAFS" 表面科学. 18. 21-28 (1997)

Gohiro Yoshida：“高度分散的负载型氧化物催化剂的 XAFS”《表面科学》18. 21-28 (1997)。