Selective Hydrodeoxygenation of Guaiacol to Phenolics by Ni/Anatase TiO2 Catalyst Formed by Cross-Surface Migration of Ni and TiO2

加氢脱氧 愈创木酚 催化作用 锐钛矿 覆盖层 初湿浸渍 无定形固体 金红石 材料科学 化学工程 无机化学 化学 有机化学 选择性 光催化 冶金 物理化学 工程类
作者
Xiaoqiang Zhang,Peifang Yan,Bin Zhao,Kairui Liu,Mayfair C. Kung,Harold H. Kung,Shanyong Chen,Z. Conrad Zhang
出处
期刊:ACS Catalysis [American Chemical Society]
卷期号:9 (4): 3551-3563 被引量:97
标识
DOI:10.1021/acscatal.9b00400
摘要

The catalytic properties of physical mixtures of Ni particles (100–200 nm) with nanoparticles of anatase TiO2 (TiO2-A), ZrO2, Al2O3, rutile TiO2 (TiO2-R), and CeO2 were investigated for the hydrodeoxygenation (HDO) of guaiacol. High selectivities to phenolics were obtained only for Ni mixed with anatase TiO2 (Ni and TiO2-A), while saturated hydrocarbons were the main products for the mixtures with other supports. By thermal treatment in hydrogen gas only at 300 °C or higher and subsequently separating the large Ni particles from the TiO2-A particles with a magnet, it was further discovered that there was migration of TiO2 from TiO2-A onto the large Ni particles, resulting in an amorphous TiO2 overlayer on the Ni particles as evidenced by high-resolution TEM, and vice versa, migration of Ni onto TiO2-A. The TiO2 overlayer rendered the Ni particles completely inactive as a hydrogenation/hydrodeoxygenation catalyst. Conversely, the small amounts of Ni (<1.5 wt %) migrated onto TiO2-A formed highly dispersed Ni, undetectable by high-resolution TEM (<2 nm), that were remarkably highly active for HDO of guaiacol, producing selectively phenolics. Such highly selective HDO catalysts could also be formed by incipient wetness impregnation of Ni in loadings above 2 wt % onto the TiO2-A, but it was essential to pretreat the sample in H2 at 300 °C or higher. Pretreatment in H2 at 200 °C generated catalysts that produced saturated ring products. The activity of the impregnated catalysts, as measured by guaiacol conversion, increased linearly with Ni loading below 0.5 wt %. The activity continued to increase with Ni loading but more slowly up to 2 wt %, beyond which there was little further change. The results suggested that two types of Ni species existed on the TiO2-A surface. One type consisted of a cluster of Ni atoms that were dominant on larger Ni particles that were active in aromatic ring hydrogenation and hydrodeoxygenation. They were readily covered by reducible TiO2-A at 300 °C or higher due to the traditional strong metal support interaction (SMSI) effect and became inactive. Another type was clusters of a very small number of Ni atoms, perhaps one atom, that were present as highly dispersed Ni clusters interacting strongly with the defect sites of TiO2-A. The strong interaction of this type of Ni with the TiO2 defect deterred TiOx migration allowing surface exposed Ni atoms to catalyze the HDO of guaiacol with very high selectivities that were not characteristic of typical Ni particles.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
阿玛特拉斯完成签到,获得积分10
刚刚
2秒前
CC关注了科研通微信公众号
4秒前
msp发布了新的文献求助10
5秒前
LY完成签到,获得积分10
5秒前
6秒前
宋笨笨完成签到 ,获得积分10
7秒前
7秒前
1x3发布了新的文献求助10
8秒前
Sam完成签到,获得积分10
11秒前
于雷是我完成签到,获得积分10
12秒前
yqz发布了新的文献求助30
13秒前
15秒前
香蕉觅云应助粉条采纳,获得10
17秒前
英姑应助Nicole采纳,获得10
18秒前
朴实子骞完成签到 ,获得积分10
19秒前
chenxin完成签到,获得积分10
20秒前
Iiiilr完成签到 ,获得积分10
20秒前
生动刺猬发布了新的文献求助10
20秒前
852应助小萝卜采纳,获得10
21秒前
夕阳与茶完成签到,获得积分10
21秒前
佳佳应助CyS采纳,获得10
21秒前
22秒前
乱武完成签到,获得积分10
22秒前
Aloha完成签到,获得积分10
23秒前
24秒前
11应助夕阳与茶采纳,获得10
25秒前
HJJHJH发布了新的文献求助50
26秒前
27秒前
eeeating完成签到,获得积分10
28秒前
田様应助notsoeasy采纳,获得10
29秒前
刘旋发布了新的文献求助10
29秒前
和谐绍辉完成签到,获得积分20
29秒前
科研通AI2S应助CyS采纳,获得10
29秒前
CC发布了新的文献求助10
29秒前
30秒前
张雷应助1x3采纳,获得20
30秒前
32秒前
帅气访天完成签到,获得积分10
32秒前
小萝卜发布了新的文献求助10
34秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
Picture Books with Same-sex Parented Families: Unintentional Censorship 700
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
Nucleophilic substitution in azasydnone-modified dinitroanisoles 500
不知道标题是什么 500
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3976210
求助须知:如何正确求助?哪些是违规求助? 3520366
关于积分的说明 11203088
捐赠科研通 3256965
什么是DOI,文献DOI怎么找? 1798570
邀请新用户注册赠送积分活动 877738
科研通“疑难数据库(出版商)”最低求助积分说明 806516