开心果壳基碳点的合成及其对Q235碳钢的缓蚀行为研究

doi:10.11949/0438-1157.20230555

摘要/Abstract

摘要：

为实现废弃果壳的合理利用及绿色缓蚀剂的制备，采用水热法分别合成了开心果壳碳点（pvs-CDs）及开心果壳-酒石酸复合碳点（pt-CDs），通过傅里叶红外光谱、X射线电子能谱、透射电子显微镜及荧光光谱对所制备的碳点进行表征，以电化学方法及失重法测试其缓蚀性能。结果表明，所制备的碳点对Q235碳钢在1 mol·L^-1盐酸中的缓蚀效率均达90.0%以上，其中pt-CDs缓蚀性能更为优异。电化学阻抗谱表明pt-CDs对浸泡6 h后碳钢的缓蚀效率可达94.5%，这主要归因于其在碳钢表面吸附形成保护膜，显著增加了碳钢腐蚀反应活化能。同时荧光光谱和差分紫外光谱法证实pt-CDs与Fe³⁺的强相互作用，可进一步促进其在碳钢表面的吸附，这为探索生物质碳点类缓蚀剂的研究提供了思路。

关键词: 生物质, 碳点, 腐蚀, 纳米材料, Q235碳钢

Abstract:

To achieve the sustainable utilization of waste shells and develop eco-friendly carbon dots (CDs) corrosion inhibitors, the pistachio shell carbon dot (pvs-CDs) and pistachio shell-tartaric acid carbon dot (pt-CDs) were synthesized. The as-prepared CDs were characterized by using Fourier infrared spectroscopy, X-ray electron spectroscopy, transmission electron microscopy and fluorescence spectroscopy. The corrosion inhibition properties of synthesized CDs were evaluated by the electrochemical method. The results show that the corrosion inhibition efficiency of the prepared carbon dots on Q235 carbon steel in 1 mol·L^-1 hydrochloric acid is above 90.0%, and the corrosion inhibition performance of pt-CDs is more excellent. Electrochemical impedance spectroscopy showed that the corrosion inhibition efficiency of pt-CDs on carbon steel after soaking for 6 h could reach 94.5%, which was mainly due to the formation of a protective film on the surface of carbon steel, which significantly increased the activation energy of corrosion reaction of carbon steel. The superior corrosion inhibition performance of pt-CDs can be attributed to the formation of a protective film on the surface of carbon steel, which is facilitated by the strong adsorption ability of pt-CDs. The established film effectively increases the activation energy of the carbon steel corrosion reaction, leading to superior corrosion inhibition properties. Fluorescence spectroscopy and differential UV-Vis spectra analyses were performed to investigate the interaction between pt-CDs and Fe³⁺, which can significantly enhance the adsorption of pt-CDs onto the carbon steel surface. This study will provide an idea to explore the research of biomass CDs-based corrosion inhibitors.

Key words: biomass, carbon dots, corrosion, nanomaterials, Q235 carbon steel

中图分类号:

TG 174.42

陈佳起, 赵万玉, 姚睿充, 侯道林, 董社英. 开心果壳基碳点的合成及其对Q235碳钢的缓蚀行为研究[J]. 化工学报, 2023, 74(8): 3446-3456.

Jiaqi CHEN, Wanyu ZHAO, Ruichong YAO, Daolin HOU, Sheying DONG. Synthesis of pistachio shell-based carbon dots and their corrosion inhibition behavior on Q235 carbon steel[J]. CIESC Journal, 2023, 74(8): 3446-3456.

图/表 10

图1 pvs-CDs、ta-CDs和pt-CDs的荧光光谱图和TEM谱图

Fig.1 Fluorescence spectra and TEM images of pvs-CDs, ta-CDs and pt-CDs

图2 pvs-CDs、ta-CDs和pt-CDs的红外光谱图

Fig.2 Infrared spectra of pvs-CDs, ta-CDs and pt-CDs

图3 pt-CDs、pvs-CDs和ta-CDs的XPS及C 1s、O 1s的高分辨谱图

Fig.3 XPS spectra of pt-CDs, pvs-CDs, ta-CDs, and their high-resolution images of C 1s and O 1s

图4 所制备CDs的缓蚀性能测试结果

Fig.4 Corrosion inhibition performance test result of the as-prepared CDs

表1 不同pt-CDs浓度下的极化曲线参数

Table 1 Polarization curve parameters at different pt-CDs concentrations

C/ (mg·L^-1)	E_corr/ V	β_a/(mV·dec^-1)	β_c/(mV·dec^-1)	I_corr/ (A·cm^-2)	η/%
0	-0.464	9.762	8.752	6.80×10^-4	—
10	-0.471	14.801	8.893	2.27×10^-4	66.6
50	-0.472	14.345	9.037	8.54×10^-5	87.4
100	-0.470	16.093	9.385	6.02×10^-5	91.1
200	-0.471	14.489	7.522	6.09×10^-5	91.0
300	-0.463	13.289	7.391	5.57×10^-5	91.8

表2 不同浸泡时间下的阻抗参数

Table 2 Impedance parameters at different immersion times

Time/h	R_s/ (Ω·cm²)	R_ct/ (Ω·cm²)	C_dl/ (μF·cm^-2)	n	η/%
0	4.9	346.4	112.84	0.81	90.2
2	2.0	375.4	82.03	0.86	90.9
6	1.2	622.6	68.19	0.89	94.5
12	2.4	381.3	79.97	0.85	91.1
24	4.1	197.2	101.87	0.84	82.7

表3 失重法数据

Table 3 Weightless method data

C/(mg·L^-1)	C_R/(g·m^-2·h^-1)				η/%
C/(mg·L^-1)	303 K	308 K	313 K	323 K	303 K	308 K	313 K	323 K
0	0.348	0.608	1.099	2.049	—	—	—	—
100	0.037	0.115	0.306	1.088	89.3	81.1	72.1	46.9
200	0.029	0.083	0.216	0.859	91.7	86.3	80.3	58.1
250	0.023	0.055	0.168	0.707	93.3	91.0	84.7	65.5
300	0.019	0.045	0.149	0.598	94.4	92.5	86.4	70.8

图5 pt-CDs的吸附等温模型、Arrhenius及过渡态理论图

Fig.5 Adsorption isotherm model, Arrhenius, and transition state theory diagram for pt-CDs

图6 pt-CDs缓蚀机理相关图

Fig.6 Correlation diagram of corrosion inhibition mechanism of pt-CDs

图7 碳钢腐蚀表面测试结果

Fig.7 Carbon steel corrosion surface test result

参考文献 35

1	Wang B Y, Waterhouse G I N, Lu S Y. Carbon dots: mysterious past, vibrant present, and expansive future[J]. Trends in Chemistry, 2023, 5(1): 76-87.
2	He Z G, Sun Y D, Zhang C, et al. Recent advances of solvent-engineered carbon dots: a review[J]. Carbon, 2023, 204: 76-93.
3	Ryplida B, Lee G, In I, et al. Zwitterionic carbon dot-encapsulating pH-responsive mesoporous silica nanoparticles for NIR light-triggered photothermal therapy through pH-controllable release[J]. Biomaterials Science, 2019, 7(6): 2600-2610.
4	Shi B B, Pang X, Wu H, et al. Ultra-robust, highly proton-conductive polymer carbon dot membranes through bioinspired complexation[J]. Journal of Materials Chemistry A, 2022, 10(32): 16995-17000.
5	Xiao Q, Lu S Y, Huang C S, et al. Novel N-doped carbon dots/ β-cyclodextrin nanocomposites for enantioselective recognition of tryptophan enantiomers[J]. Sensors, 2016, 16(11): 1874.
6	Zhao M, Zhang J J, Xiao H, et al. Facile in situ synthesis of a carbon quantum dot/graphene heterostructure as an efficient metal-free electrocatalyst for overall water splitting[J]. Chemical Communications, 2019, 55(11): 1635-1638.
7	Song Y, Zhu C Z, Song J H, et al. Drug-derived bright and color-tunable N-doped carbon dots for cell imaging and sensitive detection of Fe³⁺ in living cells[J]. ACS Applied Materials & Interfaces, 2017, 9(8): 7399-7405.
8	Yuan T, Yuan F L, Sui L Z, et al. Carbon quantum dots with near-unity quantum yield bandgap emission for electroluminescent light-emitting diodes[J]. Angewandte Chemie International Edition, 2023, 62(20): e202218568.
9	Cui M J, Ren S M, Xue Q J, et al. Carbon dots as new eco-friendly and effective corrosion inhibitor[J]. Journal of Alloys and Compounds, 2017, 726: 680-692.
10	Wang J A, Du P, Zhao H C, et al. Novel nitrogen doped carbon dots enhancing the anticorrosive performance of waterborne epoxy coatings[J]. Nanoscale Advances, 2019, 1(9): 3443-3451.
11	Guo L, Zhu M Y, He Z Y, et al. One-pot hydrothermal synthesized nitrogen and sulfur codoped carbon dots for acid corrosion inhibition of Q235 steel[J]. Langmuir, 2022, 38(13): 3984-3992.
12	Arjeh E, Akhavan H R, Barzegar M, et al. Bio-active compounds and functional properties of pistachio hull: a review[J]. Trends in Food Science & Technology, 2020, 97: 55-64.
13	Chen C B, Dong Z L. Theoretically screening of carbon dots as corrosion inhibitor: effect of size and shape, functional group, and nitrogen doping[J]. Russian Journal of Physical Chemistry A, 2022, 96(11): 2451-2458.
14	王绍壮, 于敦喜, 李佳忆, 等. 烟气烘焙对玉米秆可磨性的影响规律研究[J]. 化工学报, 2023, 74(2): 861-870.
	Wang S Z, Yu D X, Li J Y, et al. Effects of torrefaction with flue gas on grindability of corn stalk[J]. CIESC Journal, 2023, 74(2): 861-870.
15	叶茂林, 谭烽华, 李宇萍, 等. 农林废弃物气化合成混合醇生命周期环境影响分析[J]. 化工学报, 2022, 73(3): 1369-1378.
	Ye M L, Tan F H, Li Y P, et al. Life cycle environmental impact assessment of mixed alcohol via gasification of agricultural and forestry residues and catalytic synthesis[J]. CIESC Journal, 2022, 73(3): 1369-1378.
16	Rivera-Armenta J L, Salazar-Cruz B A, Espindola-Flores A C, et al. Thermal and thermomechanical characterization of polypropylene-seed shell particles composites[J]. Applied Sciences, 2022, 12(16): 8336.
17	Akti F. Green synthesis of pistachio shell-derived biochar supported cobalt catalysts and their catalytic performance in sodium borohydride hydrolysis[J]. International Journal of Hydrogen Energy, 2022, 47(83): 35195-35202.
18	Göncü B, Gülşen H, Hoşgün E Z. Bioethanol production from pistachio (Pistacia vera L.) shells applying ozone pretreatment and subsequent enzymatic hydrolysis[J]. Environmental Technology, 2021, 42(15): 2438-2446.
19	Dolatabadi M, Naidu H, Ahmadzadeh S. A green approach to remove acetamiprid insecticide using pistachio shell-based modified activated carbon; economical groundwater treatment[J]. Journal of Cleaner Production, 2021, 316: 128226.
20	胡若欣, 宋希元, 晋卫军. 碳点和掺杂碳点的发光机理[J]. 化学传感器, 2018, 38(1): 15-38.
	Hu R X, Song X Y, Jin W J. Luminescence origination of carbon dots and doped carbon dots[J]. Chemical Sensors, 2018, 38(1): 15-38.
21	Li D Y, Wang S P, Azad F, et al. A simple method for the preparation of multi-color carbon quantum dots by using reversible regulatory color transformation[J]. Microchimica Acta, 2019, 186(9): 1-9.
22	Wang L, Li W T, Yin L Q, et al. Full-color fluorescent carbon quantum dots[J]. Science Advances, 2020, 6(40): eabb6772.
23	Li L S, Qin L, Fan X, et al. A novel and simple nitrogen-doped carbon/polyaniline electrode material for supercapacitors[J]. Frontiers of Materials Science, 2021, 15(1): 147-157.
24	Jing S S, Zhao Y S, Sun R C, et al. Facile and high-yield synthesis of carbon quantum dots from biomass-derived carbons at mild condition[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(8): 7833-7843.
25	Dang D K, Sundaram C, Ngo Y L T, et al. Pyromellitic acid-derived highly fluorescent N-doped carbon dots for the sensitive and selective determination of 4-nitrophenol[J]. Dyes and Pigments, 2019, 165: 327-334.
26	Geng B J, Hu J Y, Li Y, et al. Near-infrared phosphorescent carbon dots for sonodynamic precision tumor therapy[J]. Nature Communications, 2022, 13: 5735.
27	Milenkovic I, Algarra M, Alcoholado C, et al. Fingerprint imaging using N-doped carbon dots[J]. Carbon, 2019, 144: 791-797.
28	郑天宇, 王璐, 刘金彦, 等. 离子液体在甲醇/硫酸介质中对Q235钢表面的缓蚀性能[J]. 化工学报, 2020, 71(5): 2230-2239.
	Zheng T Y, Wang L, Liu J Y, et al. Corrosion inhibition of ionic liquids on the surface of Q235 steel in methanol/sulfuric acid medium[J]. CIESC Journal, 2020, 71(5): 2230-2239.
29	Qiang Y J, Zhang S T, Zhao H C, et al. Enhanced anticorrosion performance of copper by novel N-doped carbon dots[J]. Corrosion Science, 2019, 161: 108193.
30	罗雪, 黄海军, 罗自萍, 等. 无患子果皮提取物的纳微米聚集体对钢的高效缓蚀[J]. 化工学报, 2020, 71(10): 4760-4772.
	Luo X, Huang H J, Luo Z P, et al. High efficient corrosion inhibition of steel by nano-micro aggregates of Sapindus mukorossi Gaertn peel extracts[J]. CIESC Journal, 2020, 71(10): 4760-4772.
31	董秋辰, 张光华, 张万斌, 等. 甲基丙烯酸二甲氨基乙酯类离子液体对Q235钢的缓蚀性能[J]. 高等学校化学学报, 2019, 40(12): 2556-2565.
	Dong Q C, Zhang G H, Zhang W B, et al. Corrosion inhibition of Q235 steel by ionic liquid based on the 2-(dimethylamino)ethyl methacrylate[J]. Chemical Journal of Chinese Universities, 2019, 40(12): 2556-2565.
32	Fares M M, Maayta A K, AI-Mustafa J A. Synergistic corrosion inhibition of aluminum by polyethylene glycol and ciprofloxacin in acidic media[J]. Journal of Adhesion Science and Technology, 2013, 27(23): 2495-2506.
33	Chen Y Q, Sun X B, Pan W, et al. Fe³⁺-sensitive carbon dots for detection of Fe³⁺ in aqueous solution and intracellular imaging of Fe³⁺ inside fungal cells[J]. Frontiers in Chemistry, 2020, 7: 911.
34	Zhang S P, Jiang X, Cheng S K, et al. Enhanced scale inhibition against Ca₃(PO₄)₂ and Fe₂O₃ in water using multi-functional fluorescently-tagged antibacterial scale inhibitors[J]. Environmental Science: Water Research & Technology, 2020, 6(4): 951-962.
35	Bejinariu C, Burduhos-Nergis D P, Cimpoesu N. Immersion behavior of carbon steel, phosphate carbon steel and phosphate and painted carbon steel in saltwater[J]. Materials, 2021, 14(1): 188.

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