煤基碳量子点/氮化碳复合材料制备及其光催化还原CO2性能

doi:10.11949/0438-1157.20200096

摘要/Abstract

摘要：

以太西无烟煤为原料，采用化学氧化法制备煤基碳量子点(C-CQDs)，进一步以C-CQDs和尿素为前体，原位复合制备得到煤基碳量子点/氮化碳(C-CQDs/g-C₃N₄)复合材料。采用TEM、XRD、FT-IR、UV-Vis、PL等手段对样品结构性能进行了表征和分析，进而考察了其在光催化还原CO₂合成甲醇过程的催化性能。研究表明：C-CQDs均匀地负载在g-C₃N₄的表面，且掺杂适量的C-CQDs有利于提高C-CQDs/g-C₃N₄的光催化活性，当可见光照12 h时，其光催化还原CO₂甲醇产量最高可达28.69 μmol/(g cat)，约为相同条件下纯石墨相g-C₃N₄作用时甲醇产量的2.2倍。

关键词: 煤, 氮化碳, 催化剂, 光化学, 二氧化碳, 甲醇

Abstract:

Using Taixi anthracite as a raw material, coal-based carbon quantum dots (C-CQDs) were prepared by chemical oxidation, and C-CQDs and urea were used as precursors to prepare coal-based carbon quantum dots/carbon nitride (C-CQDs /g-C₃N₄) composite materials. The composition and structure of the samples were characterized by means of TEM, XRD, FT-IR, UV-Vis and PL respectively, and the phoyocatalytic potential were assessed in terms of reduction CO₂ into methanol under visible light irradiation. The results show that the C-CQDs were uniformly decorated on the surfaces of the C-CQDs/g-C₃N₄ composite, and the C-CQDs/g-C₃N₄ exhibited superior photoactivity, the methanol yield up to 28.69 μmol/(g cat), which is about 2.2 times in comparison with that of pure graphite carbon nitride (g-C₃N₄) in photocatalytic CO₂ reduction.

Key words: coal, g-C₃N₄, catalyst, photochemistry, carbon dioxide, methanol

中图分类号:

TM 911

张睿哲, 李可可, 张凯博, 刘薇, 郑莉思, 张亚婷. 煤基碳量子点/氮化碳复合材料制备及其光催化还原CO₂性能[J]. 化工学报, 2020, 71(6): 2788-2794.

Ruizhe ZHANG, Keke LI, Kaibo ZHANG, Wei LIU, Lisi ZHENG, Yating ZHANG. Coal-based carbon quantum dots/carbon nitride composites for photocatalytic CO₂ reduction[J]. CIESC Journal, 2020, 71(6): 2788-2794.

图/表 8

表1 太西无烟煤工业分析和元素分析

Table 1 Proximate and ultimate analysis of sample

太西煤	工业分析/%(质量)			元素分析/%(质量)
太西煤	M_ad	A_d	V_daf	C	H	N	O
原煤	1.15	3.38	8.53	93.10	3.17	0.40	3.30
脱灰煤	1.00	0.33	9.88	91.18	3.92	0.50	3.30

图1 光催化还原CO2反应装置

Fig.1 Reaction system of photocatalytic CO2 reduction

图2 C-CQDs[(a)，(b)]、g-C3N4(c)和C-CQDs/g-C3N4-3(d)的透射电镜照片

Fig.2 TEM images of C-CQDs[(a),(b)], g-C3N4 (c) and C-CQDs/g-C3N4-3 (d)

图3 g-C3N4和C-CQDs/g-C3N4-3的XRD谱图

Fig.3 XRD patterns of g-C3N4 and C-CQDs/g-C3N4-3

图4 g-C3N4和C-CQDs/g-C3N4-3的FT-IR谱图

Fig.4 FT-IR spectra of g-C3N4 and C-CQDs/g-C3N4-3

图5 g-C3N4和C-CQDs/g-C3N4-3的UV-Vis谱图

Fig.5 UV-Vis spectra of g-C3N4 and C-CQDs/g-C3N4-3

图6 g-C3N4和C-CQDs/g-C3N4-3的PL谱图

Fig.6 PL spectra of g-C3N4 and C-CQDs/g-C3N4-3

图7 g-C3N4和C-CQDs/g-C3N4的光催化还原CO2甲醇产率随光照时间的变化

Fig.7 Photocatalytic conversion of CO2 into methanol over the obtained g-C3N4 and C-CQDs/g-C3N4

参考文献 30

1	Cao S, Yu J. g-C₃N₄-based photocatalysts for hydrogen generation[J]. The Journal of Physical Chemistry Letters, 2014, 5(12): 2101-2107.
2	Liang Z Q, Sun B T, Xu X S, et al. Metallic 1T-phase MoS₂ quantum dots/g-C₃N₄ heterojunctions for enhanced photocatalytic hydrogen evolution[J]. Nanoscale, 2019, 11: 12266-12274.
3	Tong Z, Yang D, Shi J, et al. Three-dimensional porous aerogel constructed by g-C₃N₄ and graphene oxide nanosheets with excellent visible-light photocatalytic performance[J]. ACS Applied Materials & Interfaces, 2015, 7(46): 25693-25701.
4	Ong W J, Tan L L, Ng Y H, et al. Graphitic carbon nitride (g-C₃N₄)-based photocatalysts for artificial photosynthesis and environmental remediation: are we a step closer to achieving sustainability?[J]. Chem. Rev., 2016, 116(12): 7159-7329.
5	Wang J C, Yao H C, Fan Z Y, et al. Indirect Z-scheme BiOI/g-C₃N₄ photocatalysts with enhanced photoreduction CO₂ activity under visible light irradiation[J]. ACS Applied Materials & Interfaces, 2016, 8(6): 3765-3775.
6	Xue J, Ma S, Zhou Y, et al. Facile photochemical synthesis of Au/Pt/g-C₃N₄ with plasmon-enhanced photocatalytic activity for antibiotic degradation[J]. ACS Applied Materials & Interfaces, 2015, 7(18): 9630-9637.
7	柳璐, 张文, 王宇新. 石墨相氮化碳的可控制备及其在能源催化中的应用[J]. 化工学报, 2018, 69(11): 4577-4591.
	Liu L, Zhang W, Wang Y X. Graphitic carbon nitride materials: controllable preparations and applications in energy catalysis[J]. CIESC Journal, 2018, 69(11): 4577-4591.
8	Fontelles-Carceller O, Muñoz-Batista M J, Fernández-García M, et al. Interface effects in sunlight-driven Ag/g-C₃N₄ composite catalysts: study of the toluene photodegradation quantum efficiency[J]. ACS Applied Materials & Interfaces, 2016, 8(4): 2617-2627.
9	Yang X, Chen Z, Xu J, et al. Tuning the morphology of g-C₃N₄ for improvement of Z-scheme photocatalytic water oxidation[J]. ACS Applied Materials & Interfaces, 2015, 7(28): 15285-15293.
10	Zhu Y P, Ren T Z, Yuan Z Y. Mesoporous phosphorus-doped g-C₃N₄ nanostructured flowers with superior photocatalytic hydrogen evolution performance[J]. ACS Applied Materials & Interfaces, 2015, 7(30): 16850-16856.
11	Xiong T, Cen W, Zhang Y, et al. Bridging the g-C₃N₄ interlayers for enhanced photocatalysis[J]. ACS Catalysis, 2016, 6(4): 2462-2472.
12	Gu Q, Gao Z, Xue C. Self-sensitized carbon nitride microspheres for long-lasting Visible-Light-Driven hydrogen generation[J]. Small, 2016, 12(26): 3543-3549.
13	Li Q, Wang S C, Sun Z X, et al. Enhanced CH₄ selectivity in CO₂ photocatalytic reduction over carbon quantum dots decorated and oxygen doping g-C₃N₄[J]. Nano Research, 2019, 12(11): 2749-2759.
14	Zhang X, Peng T, Yu L, et al. Visible/near-infrared-light-induced H₂ production over g-C₃N₄ co-sensitized by organic dye and zinc phthalocyanine derivative[J]. ACS Catalysis, 2014, 5(2): 504-510.
15	Fu J, Yu J, Jiang C, et al. g‐C₃N₄‐based heterostructured photocatalysts[J]. Advanced Energy Materials, 2018, 8(3): 1701503.
16	何志桥, 陈锦萍, 童丽丽, 等. BiOCl/g-C₃N₄异质结催化剂可见光催化还原CO₂[J]. 化工学报, 2016, 67(11): 4634-4642.
	He Z J, Chen J P, Tong L L, et al. BiOCl/g-C₃N₄heterojunction catalyst for efficient photocatalytic reduction of CO₂[J]. CIESC Journal, 2016, 67(11): 4634-4642.
17	Liu J, Liu Y, Liu N, et al. Metal-free efficient photocatalyst for stable visible water splitting via a two-electron pathway[J]. Science, 2015, 347(6225): 970-974.
18	Fang S, Xia Y, Lv K, et al. Effect of carbon-dots modification on the structure and photocatalytic activity of g-C₃N₄[J]. Applied Catalysis B: Environmental, 2016, 185: 225-232.
19	Xu D, Cheng B, Wang W, et al. Ag₂CrO₄/g-C₃N₄/graphene oxide ternary nanocomposite Z-scheme photocatalyst with enhanced CO₂ reduction activity[J]. Applied Catalysis B: Environmental, 2018, 231: 368-380.
20	Wang R, Kong X, Zhang W, et al. Mechanism insight into rapid photocatalytic disinfection of Salmonella based on vanadate QDs-interspersed g-C₃N₄ heterostructures[J]. Applied Catalysis B: Environmental, 2018, 225: 228-237.
21	张亚婷, 周安宁, 张晓欠, 等. 以太西无烟煤为前体制备煤基石墨烯的研究[J]. 煤炭转化, 2013, 36(4): 57-61.
	Zhang Y T, Zhou A N, Zhang X Q, et al. Preparation of the graphene from Taixi anthracite[J]. Coal Conversion, 2013, 36(4): 57-61.
22	Byamba-Ochir N, Shim W G, Balathanigaimani M S, et al. Highly porous activated carbons prepared from carbon rich Mongolian anthracite by direct NaOH activation[J]. Applied Surface Science, 2016, 379: 331-337.
23	Zhang Y T, Li K K, Ren S Z, et al. Coal-derived graphene quantum dots produced by ultrasonic physical tailoring and their capacity for Cu (Ⅱ) detection[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(11): 9793-9799.
24	Hu C, Yu C, Li M, et al. Chemically tailoring coal to fluorescent carbon dots with tuned size and their capacity for Cu(II) detection[J]. Small, 2014, 10(23): 4926-4933.
25	Ye R, Xiang C, Lin J, et al. Coal as an abundant source of graphene quantum dots[J]. Nature Communications, 2013, 4: 2943.
26	Ong W J, Tan L L, Chai S P, et al. Surface charge modification via protonation of graphitic carbon nitride (g-C₃N₄) for electrostatic self-assembly construction of 2D/2D reduced graphene oxide (rGO)/g-C₃N₄ nanostructures toward enhanced photocatalytic reduction of carbon dioxide to methane[J]. Nano Energy, 2015, 13: 757-770.
27	Li Y, Zhang H, Liu P, et al. Cross-Linked g-C₃N₄/rGO nanocomposites with tunable band structure and enhanced visible light photocatalytic activity[J]. Small, 2013, 9(19): 3336-3344.
28	Luo M L, Yang Q, Liu K W, et al. Boosting photocatalytic H₂ evolution on g-C₃N₄ by modifying covalent organic frameworks (COFs)[J]. Chemical Communications, 2019, 55(41): 5829-5832.
29	Qian X Y, Meng X Q, Sun J W, et al. Salt-Assisted synthesis of 3D porous g-C₃N₄ as a bifunctional photo- and electrocatalyst[J]. ACS Applied Materials & Interfaces, 2019, 11(30): 27226-27232.
30	Zhao Y, Shalom M, Antonietti M. Visible light-driven graphitic carbon nitride (g-C₃N₄) photocatalyzed ketalization reaction in methanol with methylviologen as efficient electron mediator[J]. Applied Catalysis B: Environmental, 2017, 207: 311-315.

[1]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[2]	宋瑞涛, 王派, 王云鹏, 李敏霞, 党超镔, 陈振国, 童欢, 周佳琦. 二氧化碳直接蒸发冰场排管内流动沸腾换热数值模拟分析[J]. 化工学报, 2023, 74(S1): 96-103.
[3]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[4]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[5]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[6]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[7]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[8]	赵佳佳, 田世祥, 李鹏, 谢洪高. SiO₂-H₂O纳米流体强化煤尘润湿性的微观机理研究[J]. 化工学报, 2023, 74(9): 3931-3945.
[9]	何松, 刘乔迈, 谢广烁, 王斯民, 肖娟. 高浓度水煤浆管道气膜减阻两相流模拟及代理辅助优化[J]. 化工学报, 2023, 74(9): 3766-3774.
[10]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[11]	韩晨, 司徒友珉, 朱斌, 许建良, 郭晓镭, 刘海峰. 协同处理废液的多喷嘴粉煤气化炉内反应流动研究[J]. 化工学报, 2023, 74(8): 3266-3278.
[12]	倪文翔, 赵京, 李博, 魏小林, 吴东垠, 刘迪, 王强. 转炉煤气全干法显热回收工艺中余热锅炉积灰特性研究[J]. 化工学报, 2023, 74(8): 3485-3493.
[13]	杨菲菲, 赵世熙, 周维, 倪中海. Sn掺杂的In₂O₃催化CO₂选择性加氢制甲醇[J]. 化工学报, 2023, 74(8): 3366-3374.
[14]	洪瑞, 袁宝强, 杜文静. 垂直上升管内超临界二氧化碳传热恶化机理分析[J]. 化工学报, 2023, 74(8): 3309-3319.
[15]	李凯旋, 谭伟, 张曼玉, 徐志豪, 王旭裕, 纪红兵. 富含零价钴活性位点的钴氮碳/活性炭设计及甲醛催化氧化应用研究[J]. 化工学报, 2023, 74(8): 3342-3352.

煤基碳量子点/氮化碳复合材料制备及其光催化还原CO₂性能

Coal-based carbon quantum dots/carbon nitride composites for photocatalytic CO₂ reduction

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 30

相关文章 15

编辑推荐

Metrics

本文评价