凹凸棒石/g-C3N4复合材料的制备及其电催化析氧性能研究

doi:10.15541/jim20180373

无机材料学报 ›› 2019, Vol. 34 ›› Issue (8): 803-810.DOI: 10.15541/jim20180373 CSTR: 32189.14.10.15541/jim20180373

所属专题：电催化研究

凹凸棒石/g-C₃N₄复合材料的制备及其电催化析氧性能研究

张盛,蒋亿,纪媛媛,杜莹,盛振环,殷竟洲,李乔琦,张莉莉()

淮阴师范学院化学化工学院, 江苏省低维材料化学重点实验室, 江苏省环境工程实验室, 淮安 223300

收稿日期:2018-08-15 修回日期:2018-10-09 出版日期:2019-08-20 网络出版日期:2019-04-18
作者简介:张盛(1996-), 男, 硕士研究生. E-mail: <email>545590570@qq.com</email>
基金资助:
国家自然科学基金(51472101);江苏省六大人才高峰(JY-31);江苏省自然科学基金(BK20161305);江苏省高校大学生创新计划(201710323004Z)

Attapulgite/g-C₃N₄ Composites: Synthesis and Electrocatalytic Oxygen Evolution Property

ZHANG Sheng,JIANG Yi,JI Yuan-Yuan,DU Ying,SHENG Zhen-Huan,YIN Jing-Zhou,LI Qiao-Qi,ZHANG Li-Li()

Jiangsu Environmental Engineering Laboratory, Jiangsu Key Laboratory for Low-dimension Materials, School of Chemistry and Chemical Enginering, Huaiyin Normal University, Huaian 223300, China

Received:2018-08-15 Revised:2018-10-09 Published:2019-08-20 Online:2019-04-18
Supported by:
National Natural Science Foundation of China(51472101);The Big Six-talent project of Jiangsu Province(JY-31);Natural Science Foundation of Jiangsu Province(BK20161305);Undergraduate Innovation Program of Jiangsu Province(201710323004Z)

摘要/Abstract

摘要：

以凹凸棒石(ATP)为载体, 通过原位沉积, 结合冷冻干燥、程序焙烧工艺在其表面负载不同质量分数的类石墨相氮化碳(g-C₃N₄)薄层材料, 制备系列ATP/g-C₃N₄复合材料用于电催化析氧反应, 产物标识为ATP/g-C₃N₄-w (质量分数w = mATP: (mATP + mg-C₃N₄)=0.33、0.40、0.50、0.67), 并研究在0.1 mol/L KOH的电解液中的电催化析氧性能。结果表明: g-C₃N₄薄层通过Si-O-C键牢固负载于凹凸棒石表面, 从而有效调变g-C₃N₄表面的电子层结构, 提供更多的催化活性位点。电催化析氧测试的结果表明: ATP/g-C₃N₄-0.50具有最优的析氧催化性能, 在10 mA/cm ²电流密度下其析氧过电位为410 mV, 塔菲尔斜率为118 mV/dec, 并表现出优异的析氧稳定性。

关键词: 凹凸棒石, 石墨相氮化碳, 电催化, 析氧反应

Abstract:

A novel kind of electrocatalytic oxygen evolution catalyst was fabricated by introducing g-C₃N₄ultrathin films onto the surface of attapulgite (ATP) via a simple in-situ depositing technique, combined with freeze-drying and programmed roasting process. The obtained product was identified as ATP/g-C₃N₄. In order to achieve the best catalyst, a series of ATP/g-C₃N₄ composites with different mass fraction of ATP were obtained and marked as ATP/g-C₃N₄-w, where w represents the mass fraction of ATP (w =mATP: (mATP + mg-C₃N₄)= 0.33, 0.40, 0.50, 0.67). Results show that g-C₃N₄ thin layers are uniformly loaded onto the ATP surface via the chemical bond (Si-O-C), which is beneficial to tailor the surface electronic structure of g-C₃N₄ and provide more active sites. Their electrocatalytic oxygen evolution properties in 0.1 mol/L KOH were investigated. It is found that ATP/g-C₃N₄-0.50 presents the best oxygen evolution catalytic performance and has excellent oxygen evolution stability. Its oxygen evolution over potential is 410 mV and the Tafel slope is 118 mV/dec at a current density of 10 mA/cm ². The results suggest that ATP/ g-C₃N₄-0.50 can be used as a potential oxygen evolution catalyst.

Key words: attapulgite, g-C₃N₄, electrocatalysis, oxygen evolution veaction

中图分类号:

O469

张盛, 蒋亿, 纪媛媛, 杜莹, 盛振环, 殷竟洲, 李乔琦, 张莉莉. 凹凸棒石/g-C₃N₄复合材料的制备及其电催化析氧性能研究[J]. 无机材料学报, 2019, 34(8): 803-810.

ZHANG Sheng, JIANG Yi, JI Yuan-Yuan, DU Ying, SHENG Zhen-Huan, YIN Jing-Zhou, LI Qiao-Qi, ZHANG Li-Li. Attapulgite/g-C₃N₄ Composites: Synthesis and Electrocatalytic Oxygen Evolution Property[J]. Journal of Inorganic Materials, 2019, 34(8): 803-810.

图/表 12

图1 不同催化剂(a)和不同比例ATP/g-C3N4催化剂(b)的XRD图谱

Fig. 1 XRD patterns of different catalysts (a) and ATP/g-C3N4 with different proportions (b)

图2 不同催化剂(a)和不同比例ATP/g-C3N4催化剂(b)的红外谱图

Fig. 2 Infrared spectra of (a) different catalysts (a) and ATP/g-C3N4 with different proportions (b)

图3 ATP/g-C3N4-0.5的XPS谱图

Fig. 3 XPS spectra of ATP/g-C3N4-0.5 samples (a) Wide scan; (b) C 1s; (c) N 1s; (d) O 1s; (e) Si 2p

图4 g-C3N4(a)和ATP(b)的SEM照片; ATP/g-C3N4-0.50的SEM照片(c)和EDAX图谱(d)

Fig. 4 SEM images of g-C3N4(a) and ATP(b), SEM image (c) and (d) EDAX pattern of ATP/ g-C3N4-0.50

图5 不同样品的TG (a)和DSC (b)曲线

Fig. 5 TG (a) and DSC (b) curves of different samples

表1 各样品的比表面积

Table 1 Specific surface area of each sample

Sample	S_BET/(m²?g^-1)
ATP	190.800
g-C₃N₄	8.821
ATP/g-C₃N₄-0.33	26.980
ATP/g-C₃N₄-0.40	38.280
ATP/g-C₃N₄-0.50	53.180
ATP/g-C₃N₄-0.67	82.440

图6 催化材料的循环伏安曲线

Fig. 6 Cyclic voltammograms of catalytic materials

图7 不同比例ATP/g-C3N4复合材料及机械混合物的LSV图(a), g-C3N4与ATP/g-C3N4的LSV对比(b), ATP/g-C3N4-w的LSV图(c)和过电势趋势图(d)

Fig. 7 (a) LSV of ATP/g-C3N4-w and mechanical mixture, (b) LSV of g-C3N4 and ATP/g-C3N4, (c) LSV and the over potential (d) of ATP/g-C3N4-w

表2 催化剂在10 mA/cm2下的析氧过电位E(V vs RHE)和过电势及Tafel曲线的斜率

Table 2 Oxygen evolution overpotential E(V vs RHE) and overpotential of the catalyst at 10 mA/cm2 and the slope of the Tafel curve

Sample	E/V(vs RHE)	η/mV	Tafel slope/(mV?dec^-1)
g-C₃N₄	1.73	500	155
ATP/g-C₃N₄-0.67	1.68	450	175
ATP/g-C₃N₄-0.50	1.64	410	118
ATP/g-C₃N₄-0.40	1.65	420	128
ATP/g-C₃N₄-0.33	1.69	460	143

图8 g-C3N4和不同比例的凹凸棒石ATP/g-C3N4的Tafel曲线

Fig. 8 Tafel curves of g-C3N4 and ATP/g-C3N4-w

图9 为析氧阳极材料的EIS曲线

Fig. 9 EIS curves of the oxygen evolution anode material

图10 ATP/g-C3N4-0.50恒电势电解的I-t 曲线

Fig. 10 I-t curve of constant potential electrolysis of ATP/g-C3N4-0.50

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凹凸棒石/g-C₃N₄复合材料的制备及其电催化析氧性能研究

Attapulgite/g-C₃N₄ Composites: Synthesis and Electrocatalytic Oxygen Evolution Property

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