镍铁水滑石/聚S,S-二氧-二苯并噻吩复合材料的合成及其光催化产氢性能

罗旌崧; 付清瑶; 刘玉祥; 汪锋

doi:10.13801/j.cnki.fhclxb.20211207.001

镍铁水滑石/聚S,S-二氧-二苯并噻吩复合材料的合成及其光催化产氢性能

doi: 10.13801/j.cnki.fhclxb.20211207.001

武汉工程大学　化工与制药学院，武汉 430205

基金项目: 湖北省教育厅重点项目(D20181505)；光电化学材料与器件教育部重点实验室(江汉大学)(JDGD-202003)

详细信息

通讯作者:
汪锋，博士，教授，博士生导师，研究方向为光催化材料　E-mail: psfwang@wit.edu.cn

中图分类号: O644.1
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出版历程
- 收稿日期: 2021-09-22
- 修回日期: 2021-11-09
- 录用日期: 2021-11-26
- 网络出版日期: 2021-12-08
- 刊出日期: 2022-12-01

Synthesis and photocatalytic hydrogen production performance of nickel-iron hydrotalcite/poly(dibenzothiophene-S,S-dioxide)composites

School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430205, China

摘要

摘要: 镍铁水滑石(LDH)(Ni₇Fe₁)易于合成、来源丰富、价格低廉，是目前催化体系中性能优良的催化剂之一，可望用于替代成本高昂的贵金属催化剂。采用原位聚合法将二维层状结构的Ni₇Fe₁与聚S,S-二氧-二苯并噻吩(PDBTSO)复合，制备了无机/有机复合材料Ni₇Fe₁/PDBTSO，并验证了其光催化性能。实验得到：复合材料15-Ni₇Fe₁/PDBTSO相较于添加3wt% Pt助催化剂PDBTSO的光催化产氢效率提高了22.6%，其产氢效率达到36.8 mmol·g⁻¹·h⁻¹且具有良好的循环稳定性，表明Ni₇Fe₁为替代光催化制氢反应中贵金属助催化剂理想的候选材料之一。结合XRD、FTIR、TEM和XPS等手段进一步讨论了复合材料光催化产氢的机制。Ni₇Fe₁/PDBTSO高效的光催化制氢性能及低成本的制备方法为光催化制氢领域提供了新的思路。
- 光催化 /
- 聚S,S-二氧-二苯并噻吩 /
- 氢气 /
- 水滑石 /
- 复合材料
Abstract: Two-dimensional layered double hydroxide (LDH) of Ni₇Fe₁ is the most excellent catalyst in the catalytic system for its facile preparation, abundant sources, and low-cost, which is also an ideal substitute for noble metal catalyst in photocatalytic production. In this study, we prepared composites of Ni₇Fe₁/PDBTSO by in-situ polymerization of Ni₇Fe₁ and poly(dibenzothiophene-S,S-dioxide) (PDBTSO). Furthermore, we investigated their catalytic performance. The experimental results show that 15-Ni₇Fe₁/PDBTSO exhibites the hydrogen generation rate of 36.8 mmol·g⁻¹·h⁻¹, which is 22.6% higher than that of PDBTSO with 3wt% Pt as co-catalyst. Besides, 15-Ni₇Fe₁/PDBTSO shows good photocatalytic stability, making it an ideal candidate for photocatalytic hydrogen production. XRD, FTIR, TEM and XPS were used to explore the mechanism of photocatalytic hydrogen production performance. The high photocatalytic efficiency and low cost of Ni₇Fe₁/PDBTSO provide a new idea for the field of photocatalytic hydrogen production.
- photocatalysis /
- poly(dibenzothiophene-S,S-dioxide) /
- hydrogen /
- layered double hydroxide /
- composite

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图 1 Ni₇Fe₁/聚S,S-二氧-二苯并噻吩(PDBTSO)的合成路线

Figure 1. Synthetic route for Ni₇Fe₁/poly(dibenzothiophene-S,S-dioxide) (PDBTSO)

DMF—Dimethyl formamide

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图 2 Ni₇Fe₁、PDBTSO和Ni₇Fe₁/PDBTSO的XRD图谱

Figure 2. XRD patterns of Ni₇Fe₁, PDBTSO and Ni₇Fe₁/PDBTSO

In X-Ni₇Fe₁/PDBTSO, X—Mass fraction of Ni₇Fe₁ in Ni₇Fe₁/PDBTSO

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图 3 Ni₇Fe₁、PDBTSO和Ni₇Fe₁/PDBTSO的FTIR图谱

Figure 3. FTIR spectra of Ni₇Fe₁, PDBTSO and Ni₇Fe₁/PDBTSO

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图 4 Ni₇Fe₁ (a)、PDBTSO (b)和15-Ni₇Fe₁/PDBTSO (c)的SEM图像；(d) 15-Ni₇Fe₁/PDBTSO的EDX图谱；((e)~(i)) C、O、S、Ni和Fe元素分布图

Figure 4. SEM images of PDBTSO (a), Ni₇Fe₁ (b) and 15-Ni₇Fe₁/PDBTSO(c); (d) EDX image of a single 15-Ni₇Fe₁/PDBTSO and multi-elemental image of C (e), O (f), S (g), Ni (h), Fe (i) elemental maps

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图 5 Ni₇Fe₁ (a)、15-Ni₇Fe₁/PDBTSO (b)的TEM图像；Ni₇Fe₁(c) 和15-Ni₇Fe₁/PDBTSO (d) 的HRTEM图像

Figure 5. TEM images of Ni₇Fe₁ (a) and15-Ni₇Fe₁/PDBTSO (b); HRTEM images of Ni₇Fe₁ (c) and15-Ni₇Fe₁/PDBTSO (d)

d—Distance between two parallel crystal planes

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图 6 (a) 15-Ni₇Fe₁/PDBTSO的XPS全谱图； C1s (b)、O1s (c)、S2p (d)、Ni2p (e)、Fe2p (f)的XPS谱图

Figure 6. (a) XPS spectra of 15-Ni₇Fe₁/PDBTSO and comparison results of the deconvoluted XPS spectra of Ni₇Fe₁, PDBTSO and 15-Ni₇Fe₁/PDBTSO for C1s (b), O1s (c), S2p (d), Ni2p (e), Fe2p (f)

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图 7 Ni₇Fe₁，PDBTSO和Ni₇Fe₁/PDBTSO紫外-可见光固体紫外漫反射吸收光谱图

Figure 7. UV-DRS of Ni₇Fe₁, PDBTSO and Ni₇Fe₁/PDBTSO

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图 8 Ni₇Fe₁/PDBTSO (a)、PDBTSO添加3wt%Pt助催化剂和15-Ni₇Fe₁/PDBTSO (b) 的光催化产氢性能；(c) 15-Ni₇Fe₁/PDBTSO光催化制氢稳定性测试；光催化反应前后15-Ni₇Fe₁/PDBTSO的XRD图谱 (d)、FTIR图谱 (e) 和UV-DRS图谱(f)

Figure 8. Hydrogen evolution reactions of Ni₇Fe₁/PDBTSO (a), PDBTSO with 3wt%Pt and 15-Ni₇Fe₁/PDBTSO (b); (c) Stability test of 15-Ni₇Fe₁/PDBTSO photocatalytic reaction; XRD patterns (d), FTIR spectra (e) and UV-DRS spectra (f) of 15-Ni₇Fe₁/PDBTSO before and after photocatalytic reaction

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图 9 PDBTSO和15-Ni₇Fe₁/PDBTSO的稳态荧光光谱图 (a) 和荧光寿命图 (b)；(c) Ni₇Fe₁、PDBTSO和15-Ni₇Fe₁/PDBTSO的EIS图谱；(d) PDBTSO和15-Ni₇Fe₁/PDBTSO的光电流响应图谱

Figure 9. Photoluminescence spectroscopy spectra (a) and time-resolved PL spectra (b) of PDBTSO and 15-Ni₇Fe₁/PDBTSO; (c) EIS spectra of Ni₇Fe₁, PDBTSO and 15-Ni₇Fe₁/PDBTSO; (d) Photoelectrode transient photocurrent response image of PDBTSO and 15-Ni₇Fe₁/PDBTSO

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图 10 (a) Ni₇Fe₁和PDBTSO的伏安(CV)曲线； (b) Ni₇Fe₁/PDBTSO的产氢机制图

Figure 10. (a) Current-vlotage (CV) curves of Ni₇Fe₁ and PDBTSO; (b) Proposed mechanism for photocatalytic hydrogen evolution at the Ni₇Fe₁/PDBTSO composite

CB—Conduction band; VB—Valence band; E_g—Optical band gaps; TEOA—Triethanolamine; LUMO—Lowest unoccupied molecular orbital; HOMO—Highest occupied molecular orbital

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表 1 PDBTSO和15-Ni₇Fe₁/PDBTSO荧光寿命

Table 1. Fitted decay time of the PDBTSO and 15-Ni₇Fe₁/PDBTSO

Sample	τ₁/ns	Rel/%	τ₂/ns	Rel/%	τ₃/ns	Rel/%	τ/ns
PDBTSO	0.291	43.68	0.767	31.62	2.946	24.70	0.502
15-Ni₇Fe₁/PDBTSO	0.468	53.54	2.122	37.30	8.252	9.16	0.751
Notes: τ₁, τ₂, τ₃—Fitted fluorescence lifetime value; τ—Average lifetime; Rel—Related function.

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表 2 Ni₇Fe₁和PDBTSO的光化学性能

Table 2. Optical and electrochemical properties for the PDBTSO and Ni₇Fe₁

Sample	Reduction potential/eV	Oxidation potential/eV	E_LUMO(CB)/eV	E_HOMO(VB)/eV	E_g^a/eV	E_g^b/eV
PDBTSO	−1.15	1.51	−3.35	−6.01	2.66	2.55
Ni₇Fe₁	−0.65	1.60	−3.86	−6.11	2.25	2.20
Notes: E_LUMO(CB)—Conduction band potential; E_HOMO(VB)—Valence band potential; E_g^a—Band gaps calculated from E_LUMO(CB)-E_HOMO(VB); E_g^b—Optical band gaps; E_g^b=1240/λ.

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