Pt修饰(001)面主导N掺锐钛矿TiO_2多级球的合成及光催化制氢性能
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- 英文论文题名：Pt modified N-doped anatase TiO_2 hierarchical spheres with dominant(001)facets for high-performance photocatalytic H_2 production
- 论文作者：吴宁安 ; 钟丽 ; 张慧
- 英文论文作者：Ningan Wu ; Li Zhong ; Hui Zhang ; State Key Laboratory of Chemical Resource Engineering ; Beijing University of Chemical Technology
- 年：2016
- 作者机构：北京化工大学化工资源有效利用国家重点实验室;
- 论文关键词：N掺杂TiO2 ; (001)面暴露 ; 多级纳米片介孔球 ; Pt修饰 ; 光催化制氢
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第二十七分会：光化学
- 语种：中文
- 分类号：O643.36;TQ116.2
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第二十七分会 ; 光化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：162k
- 原文格式：D
- 会议级别：全国
摘要
随着全球能源与环境问题的日益严峻,光催化剂TiO_2因稳定、无毒及活性高等优势而引起了人们广泛的关注。Yang等[1]首次以溶剂热法成功制得47%(001)面暴露率的锐钛矿TiO2单晶片,紫外光下具有良好的光催化性能,但对可见光几乎无响应。通过N掺杂可降低TiO_2禁带宽度从而提高在Pt参与下的可见光催化制氢活性,但N掺杂的锐钛矿TiO_2多存在(001)面暴露率低、颗粒尺寸大且需使用含氟盖帽剂等缺点~([2])。本文采用绿色简便的无氟溶剂热法制备得到系列~92%(001)面暴露率的N掺杂锐钛矿TiO2多级纳米片介孔球x NT-(001)-24(x=N/Ti投料摩尔比0,0.12,0.3,反应24 h),SEM、XRD及BET分析表明,三个催化剂均为超薄(~9 nm)纳米片组成的多级球(400~(-1)000 nm)、均具有超细的晶粒尺寸(D200为10.0,12.3,12.1 nm)、均匀的介孔分布(rp:3.85,2.76,4.60 nm)和较高的比表面积(124.0,142.0,110.4 m2/g)。XPS结果表明N元素掺杂进入0.12NT-(001)-24和0.3NT-(001)-24的间隙位(N/Ti(at.%)=0.054,0.080),UV-Vis DRS证明随着N掺杂量增加,催化剂的带隙能(3.18,3.04,3.03 e V)变窄。通过原位光还原沉积法在其表面负载Pt(理论负载量1.71wt%),发现0.12NT-(001)-24在甲醇/水溶液中光催化制氢的速率最高,为1.8 mmol h~(-1) g~(-1)(UV-Vis:320-780nm),远高于P25催化剂,且明显优于0.4 wt%Pt/TiO2(1.33 mmol h~(-1) g~(-1))[3]及N-TiO2(0.15 mmol h~(-1) g~(-1))[4],归因于0.12NT-(001)-24催化剂高的(001)面暴露率、最高的比表面积与N掺杂后明显变窄的禁带宽度。
In the present work, N-doped anatase TiO_2 hierarchical mesoporous spheres(xNT-(001)-24, x: theoretical nN/nTi = 0, 0.12, 0.3, reaction time: 24 h) with ca. 92% exposed(001) facets have been synthesized via a facile fluorine-free one-pot solvothermal route. The x NT-(001)-24 hierarchical spheres(400~(-1)000 nm) consist of ultrathin nanosheets(~9 nm) have small crystallite sizes(D_(200)=10.0, 12.3, 12.1 nm), uniform mesoporous distribution(2~(-1)0 nm) and high specific surface area(124.0, 142.0, 110.4 m~2/g). XPS result indicates N atoms(actual n_N/n_(Ti) = 0.054, 0.080) are successfully incorporated into interstitial sites of TiO_2 crystal lattices. UV-vis DRS shows the bandgap energies(3.18, 3.04, 3.03 e V) of samples are reduced with increasing nN/nTi. Pt nanoparticles(theoretical loading: 1.71 wt%) are then loaded onto the surface of x NT-(001)-24 hierarchical spheres by in situ photodeposition method. 0.12NT-(001)-24 exhibits the highest efficiency for photocatalytic hydrogen production of 1.8 mmol·h~(-1)·g~(-1), much higher than P_(25) and the previously reported 0.4 wt% Pt/TiO_2(1.33 mmol h~(-1) g~(-1))[3] and N-TiO2(0.15 mmol h~(-1) g~(-1)),[4] owing to its large percentage of(001) facets, highest specific surface area, and narrow band gap.
In the present work, N-doped anatase TiO_2 hierarchical mesoporous spheres(xNT-(001)-24, x: theoretical nN/nTi = 0, 0.12, 0.3, reaction time: 24 h) with ca. 92% exposed(001) facets have been synthesized via a facile fluorine-free one-pot solvothermal route. The x NT-(001)-24 hierarchical spheres(400~(-1)000 nm) consist of ultrathin nanosheets(~9 nm) have small crystallite sizes(D_(200)=10.0, 12.3, 12.1 nm), uniform mesoporous distribution(2~(-1)0 nm) and high specific surface area(124.0, 142.0, 110.4 m~2/g). XPS result indicates N atoms(actual n_N/n_(Ti) = 0.054, 0.080) are successfully incorporated into interstitial sites of TiO_2 crystal lattices. UV-vis DRS shows the bandgap energies(3.18, 3.04, 3.03 e V) of samples are reduced with increasing nN/nTi. Pt nanoparticles(theoretical loading: 1.71 wt%) are then loaded onto the surface of x NT-(001)-24 hierarchical spheres by in situ photodeposition method. 0.12NT-(001)-24 exhibits the highest efficiency for photocatalytic hydrogen production of 1.8 mmol·h~(-1)·g~(-1), much higher than P_(25) and the previously reported 0.4 wt% Pt/TiO_2(1.33 mmol h~(-1) g~(-1))[3] and N-TiO2(0.15 mmol h~(-1) g~(-1)),[4] owing to its large percentage of(001) facets, highest specific surface area, and narrow band gap.
引文
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[2]Zhou,X.,Peng,F.,Wang,H.,Yu,H.,et al,Chem.Commun.,2012,48(4):600-602.
[3]Li H.Y,Yu H.W.,Sun L.,Zhai J.L.,et al,Nanoscale,2015,7:1610-1615.
[4]Liu G,Yang H.G.,Wang X.W,Lu G.Q.,et al,J.Am.Chem.Soc.,2009,131:12868-12869.