非贵金属Co5.47N/N-rGO助催化剂增强TiO2光催化制氢性能

doi:10.15541/jim20210267

无机材料学报 ›› 2022, Vol. 37 ›› Issue (5): 534-540.DOI: 10.15541/jim20210267

非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能

安琳¹, 吴淏¹, 韩鑫², 李耀刚¹, 王宏志¹, 张青红¹()

1. 东华大学材料科学与工程学院纤维材料改性国家重点实验室, 上海 201620
2. 华东理工大学化工学院化学工程联合国家重点实验室, 上海 200237

收稿日期:2021-04-25 修回日期:2021-06-08 出版日期:2022-05-20 网络出版日期:2021-06-30
通讯作者: 张青红, 研究员. E-mail: zhangqh@dhu.edu.cn; 韩鑫, 讲师. E-mail: hanx@ecust.edu.cn
作者简介:安琳(1993-), 女, 博士研究生. E-mail: al1619@163.com
基金资助:
国家自然科学基金面上项目(51572046)

Non-precious Metals Co_5.47N/Nitrogen-doped rGO Co-catalyst Enhanced Photocatalytic Hydrogen Evolution Performance of TiO₂

AN Lin¹, WU Hao¹, HAN Xin², LI Yaogang¹, WANG Hongzhi¹, ZHANG Qinghong¹()

1. State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
2. State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2021-04-25 Revised:2021-06-08 Published:2022-05-20 Online:2021-06-30
Contact: ZHANG Qinghong, professor. E-mail: zhangqh@dhu.edu.cn; HAN Xin, lecturer. E-mail: hanx@ecust.edu.cn
About author:AN Lin (1993-), female, PhD candidate. E-mail: al1619@163.com
Supported by:
National Natural Science Foundation of China(51572046)

摘要/Abstract

摘要：

高效稳定的光催化剂或助催化剂研究一直是光催化领域的重要课题之一。本研究以氧化石墨烯、氯化钴和2-甲基咪唑为前驱体, 结合液相法和氨气氮化法制备了负载Co_5.47N的氮掺杂还原氧化石墨烯(Co_5.47N/N-rGO), 其中Co_5.47N高度分散、晶粒尺寸为10~20 nm。Co_5.47N/N-rGO可以作为助催化剂有效地改善商业二氧化钛(P25)的光催化分解水制氢性能, 当其质量分数为25%时, 催化剂的制氢性能可以达到11.71 mmol·h ^-1·g ^-1, 相比于纯P25提升了90倍, 与负载贵金属Pt的性能相当(11.88 mmol·h ^-1·g ^-1), 并且具有良好的稳定性。本研究为高效非贵金属助催化剂的研制提供了新思路。

关键词: Co_5.47N, 氮掺杂石墨烯, TiO₂, 光催化制氢, 助催化剂

Abstract:

Developing a highly efficient and stable photocatalyst or co-catalyst is one of the important topics in the field of photocatalysis research. In this study, graphene oxide, cobalt chloride and 2-methylimidazole were used as precursors to prepare Co_5.47N-loaded nitrogen-doped reduced graphene oxide (Co_5.47N/N-rGO) co- catalyst by combining liquid phase method and nitridation in flowing NH₃ where Co_5.47N with a crystallite size of 10~20 nm was highly dispersed over N-rGO surface. The Co_5.47N/N-rGO co-catalyst significantly improves the hydrogen evolution performance of commercial nano TiO₂ (P25). When the mass percent of Co_5.47N/N-rGO was 25%, the hydrogen evolution rate of the obtained sample reached 11.71 mmol·h ^-1·g ^-1, which was 90 times higher than that of pure P25 and similar to that loaded noble metal Pt (11.88 mmol·h ^-1·g ^-1). Furthermore, the catalyst also has good stability. The research provides a new idea for the future development of efficient non-precious metal co-catalysts.

Key words: Co_5.47N, nitrogen-doped graphene, TiO₂, photocatalytic hydrogen evolution, co-catalyst

中图分类号:

TQ174

安琳, 吴淏, 韩鑫, 李耀刚, 王宏志, 张青红. 非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能[J]. 无机材料学报, 2022, 37(5): 534-540.

AN Lin, WU Hao, HAN Xin, LI Yaogang, WANG Hongzhi, ZHANG Qinghong. Non-precious Metals Co_5.47N/Nitrogen-doped rGO Co-catalyst Enhanced Photocatalytic Hydrogen Evolution Performance of TiO₂[J]. Journal of Inorganic Materials, 2022, 37(5): 534-540.

图/表 7

图1 P25和P25/NGCo-x的XRD图谱

Fig. 1 XRD patterns of P25 and P25/NGCo-x

图2 P25、NGCo和P25/NGCo-x的UV-Vis漫反射吸收光谱及对应的样品照片

Fig. 2 UV-Vis diffuse reflectance absorption spectra and corresponding pictures of P25, NGCo and P25/NGCo-x

图3 P25/NGCo-25的TEM(a), HRTEM(b~e)照片及其对应的EDS元素分布图(f~j)

Fig. 3 TEM image (a), HRTEM images (b-e) and EDS elemental mappings (f-j) of P25/NGCo-25

图4 P25/NGCo-25的XPS全谱(a)和Co2p (b), C1s (c), N1s (d)的高分辨XPS分峰拟合谱

Fig. 4 XPS survey spectrum (a) and high-resolution XPS spectra of Co2p (b), C1s (c), and N1s (d) for P25/NGCo-25

图5 P25、NGCo、P25/NGCo-x、P25/Pt和P25/NG-25在全光谱照射下的制氢性能 (a)、P25/NGCo-25在不同光源照射下的制氢性能(b)、对应的制氢速率直方图(c)和P25/NGCo-25样品的循环制氢性能(d)

Fig. 5 Photocatalytic hydrogen evolution of P25, NGCo, P25/NGCo-x, P25/Pt, and P25/NG-25 under 300 W Xe lamp (a), hydrogen evolution of P25/NGCo-25 under different light sources (b), corresponding histogram of hydrogen evolution rates (c) and cycling test of P25/NGCo-25 (d)

图6 P25和P25/NGCo-25的瞬态光电流响应曲线 (a)和电化学阻抗谱图(插图为P25/NGCo-25的放大图)(b)

Fig. 6 Transient photocurrent response curves (a) and electrochemical impedance spectra (EIS) (b) of P25 and P25/NGCo-25 with inset in (b) showing an enlarged view of P25/NGCo-25

图7 P25/NGCo-x光催化制氢机理示意图

Fig. 7 Schematic diagram of photocatalytic hydrogen evolution mechanism for P25/NGCo-x

参考文献 36

[1]	ZOU C, XIONG B, XUE H,et al. The role of new energy in carbon neutral. Petroleum Exploration and Development, 2021,48(2):1-10.
[2]	FUJISHIMA A, HONDA K. Electrochemical photolysis of water at a semiconductor electrode. Nature, 1972,238(5358):37-38.
[3]	SINGH R, DUTTA S. A review on H₂ production through photocatalytic reactions using TiO₂/TiO₂-assisted catalysts. Fuel, 2018,220:607-620.
[4]	XIONG H, WU L, LIU Y,et al. Controllable synthesis of mesoporous TiO₂ polymorphs with tunable crystal structure for enhanced photocatalytic H₂ production. Advanced Energy Materials, 2019,9(31):1901634.
[5]	HAN X, AN L, XU D,et al. Mesoporous Pt/TiO₂-_xN_x nanoparticles with less than 10 nm and high specific surface area as visible light hydrogen evolution photocatalysts. Journal of Sol-Gel Science and Technology, 2018,87(1):230-239.
[6]	KUMARAVEL V, MATHEW S, BARTLETT J,et al. Photocatalytic hydrogen production using metal doped TiO₂: a review of recent advances. Applied Catalysis B: Environmental, 2019,244:1021-1064.
[7]	WANG P, LI X, SHI Z,et al. Synergistic effect of Ag and Ag₂O on photocatalytic H₂-evolution performance of TiO₂. Journal of Inorganic Materials, 2020,35(7):781-788.
[8]	TIAN H, KANG S Z, LI X,et al. Fabrication of an efficient noble metal-free TiO₂-based photocatalytic system using Cu-Ni bimetallic deposit as an active center of H₂ evolution from water. Solar Energy Materials and Solar Cells, 2015,134:309-317.
[9]	FU Y S, BI M, LI C,et al. Research progress on non-noble metal/ nitrogen-doped carbon composite materials in electrocatalytic oxygen evolution reaction. Journal of Inorganic Materials, 2022,37(2):163-172.
[10]	HOU J, LAN X, SHI J,et al. A mild and simple method to fabricate commercial TiO₂(P25) and C₆₀ composite for highly enhancing H₂ generation. International Journal of Hydrogen Energy, 2020,45(4):2852-2861.
[11]	WANG J, JIA H, GUO Y,et al. (TiO₂ (B)nanosheet)/(metallic phase MoS₂) hybrid nanostructures: An efficient catalyst for photocatalytic hydrogen evolution. Solar RRL, 2019,3(12):1900323.
[12]	NOVOSELOV K S, GEIM A K, MOROZOV S V,et al. Electric field effect in atomically thin carbon films. Science, 2004,306(5696):666-669.
[13]	MUKHERJI A, SEGER B, LU G Q(Max),et al. Nitrogen doped Sr₂Ta₂O₇ coupled with graphene sheets as photocatalysts for increased photocatalytic hydrogen production. ACS Nano, 2011,5(5):3483-3492.
[14]	ZHANG H, LV X, LI Y,et al. P25-graphene composite as a high performance photocatalyst. ACS Nano, 2010,4(1):380-386.
[15]	XIANG Q, YU J. Graphene-based photocatalysts for hydrogen generation. The Journal of Physical Chemistry Letters, 2013,4(5):753-759.
[16]	ZHENG B, WANG J, WANG F B,et al. Low-loading cobalt coupled with nitrogen-doped porous graphene as excellent electrocatalyst for oxygen reduction reaction. Journal of Materials Chemistry A, 2014,2(24):9079-9084.
[17]	ALAM Z, VERMA B, SINHA A S K. Creation of heterojunction in CdS supported on N, S-rGO for efficient charge separation for photo-reduction of water to hydrogen. International Journal of Hydrogen Energy, 2020,45(7):4095-4112.
[18]	ZHENG P, ZHOU W, WANG Y,et al. N-doped graphene-wrapped TiO₂ nanotubes with stable surface Ti³+ for visible-light photocatalysis. Applied Surface Science, 2020,512:144549.
[19]	ZHAO Q, SUN J, LI S,et al. Single nickel atoms anchored on nitrogen-doped graphene as a highly active cocatalyst for photocatalytic H₂ evolution. ACS Catalysis, 2018,8(12):11863-11874.
[20]	SADANANDAM G, LALITHA K, KUMARI V D,et al. Cobalt doped TiO₂: a stable and efficient photocatalyst for continuous hydrogen production from glycerol: water mixtures under solar light irradiation. International Journal of Hydrogen Energy, 2013,38(23):9655-9664.
[21]	MA Y T, LI Q L. Preparation and characterization of TiO₂/Co₃O₄ nanocomposites and their photocatalytic activity for hydrogen evolution. Journal of Inorganic Materials, 2016,31(8):841-844.
[22]	HAN C, ZHANG T, CAI Q,et al. 0D CoP cocatalyst/2D g-C₃N₄ nanosheets: an efficient photocatalyst for promoting photocatalytic hydrogen evolution. Journal of the American Ceramic Society, 2019,102(9):5484-5493.
[23]	CHEN H, JIANG D, SUN Z,et al. Cobalt nitride as an efficient cocatalyst on CdS nanorods for enhanced photocatalytic hydrogen production in water. Catalysis Science & Technology, 2017,7(7):1515-1522.
[24]	CAO X, WANG T, JIAO L. Transition-metal (Fe, Co, and Ni)- based nanofiber electrocatalysts for water splitting. Advanced Fiber Materials, 2021,3(4):210-228.
[25]	YI L, LAN F, LI J,et al. Efficient noble-metal-free Co-NG/TiO₂ photocatalyst for H₂ evolution: synergistic effect between single- atom Co and N-doped graphene for enhanced photocatalytic activity. ACS Sustainable Chemistry & Engineering, 2018,6(10):12766-12775.
[26]	ZHAI L F, KONG S Y, ZHANG H,et al. Facile synthesis of Co-N-rGO composites as an excellent electrocatalyst for oxygen reduction reaction. Chemical Engineering Science, 2019,194:45-53.
[27]	LIU Q, ZENG C, XIE Z,et al. Cobalt@nitrogen-doped bamboo- structured carbon nanotube to boost photocatalytic hydrogen evolution on carbon nitride. Applied Catalysis B: Environmental, 2019,254:443-451.
[28]	CHEN Z, HA Y, LIU Y,et al. In situ formation of cobalt nitrides/ graphitic carbon composites as efficient bifunctional electrocatalysts for overall water splitting. ACS Applied Materials & Interfaces, 2018,10(8):7134-7144.
[29]	ODA K, YOSHIO T, ODA K. Preparation of Co-N films by RF- sputtering. Journal of Materials Science, 1987,22(8):2729-2733.
[30]	RONG Z, DONG C, ZHANG S,et al. Co_5.47N loaded N-doped carbon as an efficient bifunctional oxygen electrocatalyst for a Zn-air battery. Nanoscale, 2020,12(10):6089-6095.
[31]	YIN D, HUANG G, SUN Q,et al. RGO/Co₃O₄ composites prepared using GO-MOFs as precursor for advanced lithium-ion batteries and supercapacitors electrodes. Electrochimica Acta, 2016,215:410-419.
[32]	XU D, LI L, HE R,et al. Noble metal-free RGO/TiO₂ composite nanofiber with enhanced photocatalytic H₂-production performance. Applied Surface Science, 2018,434:620-625.
[33]	YANG L, LIU Y, WANG L,et al. Co_5.47N/rGO@NF as a high- performance bifunctional catalyst for urea-assisted hydrogen evolution. Catalysis Letters, 2019,149(11):3111-3118.
[34]	QIAN X, WANG H, WANG R,et al. Dual-carbon coupled Co_5.47N composites for capacitive lithium-ion storage. Journal of Colloid and Interface Science, 2021,587:192-201.
[35]	LI X, ZHANG Q, WANG H,et al. (Ga₁-_xZn_x)(N_1-_xO_x)-rGO composites with enhanced photocatalytic performance for visible- light driven water splitting. Applied Surface Science, 2015,358:57-62.
[36]	HAN W, CHEN L, SONG W,et al. Synthesis of nitrogen and sulfur co-doped reduced graphene oxide as efficient metal-free cocatalyst for the photo-activity enhancement of CdS. Applied Catalysis B: Environmental, 2018,236:212-221.

非贵金属Co_5.47N/N-rGO助催化剂增强TiO₂光催化制氢性能

Non-precious Metals Co_5.47N/Nitrogen-doped rGO Co-catalyst Enhanced Photocatalytic Hydrogen Evolution Performance of TiO₂

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价

[1]	王如意, 徐国良, 杨蕾, 邓崇海, 储德林, 张苗, 孙兆奇. p-n异质结BiVO₄/g-C₃N₄光阳极的制备及其光电化学水解性能[J]. 无机材料学报, 2023, 38(1): 87-96.
[2]	陈瀚翔, 周敏, 莫曌, 宜坚坚, 李华明, 许晖. CoN/g-C₃N₄ 0D/2D复合结构及其光催化制氢性能研究[J]. 无机材料学报, 2022, 37(9): 1001-1008.
[3]	胡越, 安琳, 韩鑫, 侯成义, 王宏志, 李耀刚, 张青红. RhO₂修饰BiVO₄薄膜光阳极的制备及其光电催化分解水性能[J]. 无机材料学报, 2022, 37(8): 873-882.
[4]	吕庆洋, 张玉亭, 顾学红. 超声辅助溶胶-凝胶法制备中空纤维TiO₂超滤膜[J]. 无机材料学报, 2022, 37(10): 1051-1057.
[5]	高娃, 熊宇杰, 吴聪萍, 周勇, 邹志刚. 基于超薄纳米结构的光催化二氧化碳选择性转化[J]. 无机材料学报, 2022, 37(1): 3-14.
[6]	肖翔, 郭少柯, 丁成, 张志洁, 黄海瑞, 徐家跃. CsPbBr₃@TiO₂核壳结构纳米复合材料用作水稳高效可见光催化剂[J]. 无机材料学报, 2021, 36(5): 507-512.
[7]	席文, 李海波. TiO₂/Ti₃C₂T_x复合材料的制备及其杂化电容脱盐特性的研究[J]. 无机材料学报, 2021, 36(3): 283-291.
[8]	刘彩, 刘芳, 黄方, 王晓娟. 海藻基CDs-Cu-TiO₂复合材料的制备及其光催化性能[J]. 无机材料学报, 2021, 36(11): 1154-1162.
[9]	李翠霞, 孙会珍, 金海泽, 史晓, 李文生, 孔文慧. 3D多级孔rGO/TiO₂复合材料的构筑及其光催化性能研究[J]. 无机材料学报, 2021, 36(10): 1039-1046.
[10]	王苹,李心宇,时占领,李海涛. Ag与Ag₂O协同增强TiO₂光催化制氢性能的研究[J]. 无机材料学报, 2020, 35(7): 781-788.
[11]	季邦, 赵文锋, 段洁利, 马立哲, 付兰慧, 杨洲. 泡沫镍网负载TiO₂/WO₃薄膜对乙烯的光催化降解[J]. 无机材料学报, 2020, 35(5): 581-588.
[12]	王旭聪, 邓浩, 姜忠义, 袁立永. 不同N源无定形TiO₂/g-C₃N₄光催化还原Re(VII)性能[J]. 无机材料学报, 2020, 35(12): 1340-1348.
[13]	刘金云, 张玉亭, 洪周, 刘华, 王圣贤, 顾学红. 共挤出法制备双层中空纤维陶瓷复合膜[J]. 无机材料学报, 2020, 35(12): 1333-1339.
[14]	陈浩禹, 张亦文, 吴忠, 秦真波, 吴姗姗, 胡文彬. 强磁靶共溅射法制备具有室温磁电阻特性的Co-TiO₂纳米复合薄膜[J]. 无机材料学报, 2020, 35(11): 1263-1267.
[15]	吕喜庆, 张环宇, 李瑞, 张梅, 郭敏. Nb₂O₅包覆对TiO₂纳米阵列/上转换发光复合结构柔性染料敏化太阳能电池性能的影响[J]. 无机材料学报, 2019, 34(6): 590-598.