Preparation of N/B/Fe co-doped biochar cathode for degradation of p-nitrophenol

doi:10.16085/j.issn.1000-6613.2020-1646

Abstract

Abstract:

N/B/Fe co-doped biochar (N/B/Fe@BC) was synthesized from corncob by thermal deposition and calcination. The crystal lattice structure, morphology, composition and other properties of the sample were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) and so on. The catalytic performance in electro-Fenton system with N/B/Fe co-doped cathode was investigated using p-nitrophenol as the model pollutant. The results showed that N/B/Fe@BC had a three-dimensional porous structure with staggered accumulation of nanosheets, and its surface defects were significantly increased compared with the undoped biochar. The catalytic oxygen reduction on the N/B/Fe@BC was dominated by the production of H₂O₂via two electrons reduction. The degradation rate of p-nitrophenol could reach 97.93%±1.62% in 120min with the current intensity of 50mA and initial pH of 3, and the apparent rate constant within 60min was 0.040min^-1, which was 2.7 times higher than that of the undoped biochar cathode. The N/B/Fe@BC cathode expressed high activity in a wide pH range of 3—9 and feasibility in different water matrix including tap water, river water and municipal sewage. In addition, after ten times cycle, the degradation rate of p-nitrophenol could still reach more than 85% in 120min with the N/B/Fe@BC cathode.

Key words: N/B/Fe co-doped, biochar, corncob, electro-Fenton, p-nitrophenol

摘要：

以玉米芯为主要原料，采用热沉积、高温焙烧法，制备N/B/Fe共掺杂生物质炭（N/B/Fe@BC），通过X射线衍射（XRD）、扫描电子显微镜（SEM）、高分辨透射电子显微镜（HRTEM）和X射线光电子能谱仪（XPS）等手段对样品的晶格结构、形貌特征和组成等进行表征，并以对硝基酚为对象，探究N/B/Fe@BC电极的电芬顿催化性能。结果表明，N/B/Fe@BC为纳米薄片交错堆积的三维多孔结构，表面缺陷较未掺杂生物质炭显著增加，催化氧还原以两电子产H₂O₂为主。在电流强度50mA、初始pH为3的电芬顿体系中，120min时对硝基酚的去除率为97.93%±1.62%，60min内反应速率常数k为0.040min^-1，是未掺杂生物质炭电极的2.7倍。N/B/Fe@BC电极的pH适用范围较宽，受水质的影响较小，循环使用10次后120min对硝基酚的去除率仍可达到85%以上。

关键词: N/B/Fe共掺杂, 生物质炭, 玉米芯, 电芬顿, 对硝基酚

CLC Number:

X703.1

TANG Qian, FAN Yixin, SU Xin, HUANG Chengsi, SUN Yuwei, GAO Yonghui, WANG Dong. Preparation of N/B/Fe co-doped biochar cathode for degradation of p-nitrophenol[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 4064-4073.

汤茜, 范艺馨, 苏欣, 黄成思, 孙玉伟, 高永慧, 王栋. N/B/Fe共掺杂生物质炭阴极制备及电芬顿降解对硝基酚[J]. 化工进展, 2021, 40(7): 4064-4073.

Figures/Tables 12

References 45

1	XIONG Z K, ZHANG H, ZHANG W C, et al. Removal of nitrophenols and their derivatives by chemical redox: a review[J]. Chemical Engineering Journal, 2019, 359: 13-31.
2	XU W T, CHEN J N, QIU Y, et al. Highly efficient microwave catalytic oxidation degradation of 4-nitrophenol over magnetically separable NiCo₂O₄-Bi₂O₂CO₃ composite without adding oxidant[J]. Separation and Purification Technology, 2019, 213: 426-436.
3	SANTOS A DOS, VIANTE M F, POCHAPSKI D J, et al. Enhanced removal of p-nitrophenol from aqueous media by montmorillonite clay modified with a cationic surfactant[J]. Journal of Hazardous Materials, 2018, 355: 136-144.
4	孟启, 舒斌斌, 周峰, 等. 胺化聚苯乙烯树脂的制备及吸附对硝基酚[J]. 化工进展, 2015, 34(6):1714-1719.
	MENG Q, SHU B B, ZHOU F, et al. Preparation of aminated polystyrene resins and its adsorption of p-nitrophenol[J]. Chemical Industry and Engineering Progress, 2015, 34(6):1714-1719.
5	MEI X, LIU J, GUO Z W, et al. Simultaneous p-nitrophenol and nitrogen removal in PNP wastewater treatment: comparison of two integrated membrane-aerated bioreactor systems[J]. Journal of Hazardous Materials, 2019, 363: 99-108.
6	RODRIGUES C S D, BORGES R A C, LIMA V N, et al. p-Nitrophenol degradation by Fenton's oxidation in a bubble column reactor[J]. Journal of Environmental Management, 2018, 206: 774-785.
7	LI H Y, XING X, WANG K, et al. Improved BDD anode system in electrochemical degradation of p-nitrophenol by corroding electrode of iron[J]. Electrochimica Acta, 2018, 291: 335-342.
8	NIE Y C, YU F, WANG L C, et al. Photocatalytic degradation of organic pollutants coupled with simultaneous photocatalytic H-2 evolution over graphene quantum dots/Mn-N-TiO₂/g-C₃N₄ composite catalysts: performance and mechanism[J]. Applied Catalysis B: Environmental, 2018, 227: 312-321.
9	NIDHEESH P V, GANDHIMATHI R. Trends in electro-Fenton process for water and wastewater treatment: an overview[J]. Desalination, 2012, 299: 1-15.
10	CHEN S, TANG L, FENG H P, et al. Carbon felt cathodes for electro-Fenton process to remove tetracycline via synergistic adsorption and degradation[J]. Science of the Total Environment, 2019, 670: 921-931.
11	BRILLAS E, SIRES I, OTURAN M A. Electro-Fenton process and related electrochemical technologies based on Fenton's reaction chemistry[J]. Chemical Reviews, 2009, 109(12): 6570-6631.
12	ZHOU W, RAJIC L, CHEN L, et al. Activated carbon as effective cathode material in iron-free electro-Fenton process: integrated H₂O₂ electrogeneration, activation, and pollutants adsorption[J]. Electrochimica Acta, 2019, 296: 317-326.
13	COLADES J I, DE LUNA M D G, SECONDES M F N, et al. Electrochemical in situ hydrogen peroxide generation in a packed-bed reactor for Fenton oxidation of p-nitrophenol in aqueous solution[J]. Process Safety and Environmental Protection, 2019, 123: 161-168.
14	JIANG W L, XIA X, HAN J L, et al. Graphene modified electro-Fenton catalytic membrane for in situ degradation of antibiotic florfenicol[J]. Environmental Science & Technology, 2018, 52(17): 9972-9982.
15	DUAN X G, INDRAWIRAWAN S, SUN H Q, et al. Effects of nitrogen-, boron-, and phosphorus-doping or codoping on metal-free graphene catalysis[J]. Catalysis Today, 2015, 249: 184-191.
16	ZHAO K, QUAN X, CHEN S, et al. Enhanced electro-Fenton performance by fluorine-doped porous carbon for removal of organic pollutants in wastewater[J]. Chemical Engineering Journal, 2018, 354: 606-615.
17	FERNANDEZ-SAEZ N, VILLELA-MARTINEZ D E, CARRASCO-MARIN F, et al. Heteroatom-doped graphene aerogels and carbon-magnetite catalysts for the heterogeneous electro-Fenton degradation of acetaminophen in aqueous solution[J]. Journal of Catalysis, 2019, 378: 68-79.
18	CAO P K, ZHAO K, QUAN X, et al. Efficient and stable heterogeneous electro-Fenton system using iron oxides embedded in Cu, N co-doped hollow porous carbon as functional electrocatalyst[J]. Separation and Purification Technology, 2020, 238: 116424.
19	PREMARATHNA K S D, RAJAPAKSHA A U, SARKAR B, et al. Biochar-based engineered composites for sorptive decontamination of water: a review[J]. Chemical Engineering Journal, 2019, 372: 536-550.
20	ZHU S S, HUANG X C, MA F, et al. Catalytic removal of aqueous contaminants on N-doped graphitic biochars: inherent roles of adsorption and nonradical mechanisms[J]. Environmental Science & Technology, 2018, 52(15): 8649-8658.
21	SIZMUR T, FRESNO T, AKGUL G, et al. Biochar modification to enhance sorption of inorganics from water [J]. Bioresource Technology, 2017, 246: 34-47.
22	余剑刚, 张兴文, 王栋, 等. 水热改性热解生物炭的制备、表征及吸附特性[J]. 工业水处理, 2018, 38(9): 53-57.
	YU J G, ZHANG X W, WANG D, et al. Preparation，characterization and adsorption performance of hydrothermal modified pyrolysis biochar[J]. Industrial Water Treatment, 2018, 38(9): 53-57.
23	DENG F X, OLVERA-VARGAS H, GARCIA-RODRIGUEZ O, et al. Waste-wood-derived biochar cathode and its application in electro-Fenton for sulfathiazole treatment at alkaline pH with pyrophosphate electrolyte[J]. Journal of Hazardous Materials, 2019, 377: 249-258.
24	LIANG J X, TANG D Y, HUANG L, et al. High oxygen reduction reaction performance nitrogen-doped biochar cathode: a strategy for comprehensive utilizing nitrogen and carbon in water hyacinth[J]. Bioresource Technology, 2018, 267: 524-531.
25	ZHAO H Y, CHEN Y, PENG Q S, et al. Catalytic activity of MOF(2Fe/Co)/carbon aerogel for improving H₂O₂ and ·OH generation in solar photo-electro-Fenton process[J]. Applied Catalysis B: Environmental, 2017, 203: 127-137.
26	YUAN H R, CHEN H B, LI D N, et al. Catalytic synthesis and simultaneous co-doping of hierarchically porous carbon with in situ coated graphene from biomass tar as efficient catalyst for ORR[J]. Electrochemistry Communications, 2019, 100: 52-59.
27	SELLERS R M. Spectrophotometric determination of hydrogen peroxide using potassium titanium(Ⅳ) oxalate[J]. The Analyst, 1980, 105(1255): 950-954.
28	BABA Y, YATAGAI T, HARADA T, et al. Hydroxyl radical generation in the photo-Fenton process: effects of carboxylic acids on iron redox cycling[J]. Chemical Engineering Journal, 2015, 277: 229-241.
29	ZHAO H Y, QIAN L, CHEN Y, et al. Selective catalytic two-electron O₂ reduction for onsite efficient oxidation reaction in heterogeneous electro-Fenton process[J]. Chemical Engineering Journal, 2018, 332: 486-498.
30	JIAO Y, WAN C C, BAO W H, et al. Facile hydrothermal synthesis of Fe₃O₄@cellulose aerogel nanocomposite and its application in Fenton-like degradation of Rhodamine B[J]. Carbohydrate Polymers, 2018, 189: 371-378.
31	郭斌斌, 欧阳静, 杨华明. 埃洛石管内负载纳米四氧化三铁复合材料对亚甲基蓝的吸附性能[J]. 硅酸盐学报, 2016, 44(11): 1655-1661.
	GUO B B, OUYANG J, YANG H M. Adsorption performance to methylene blue by nano-Fe₃O₄ assembled in lumen of halloysite nanotubes[J]. Journal of the Chinese Ceramic Society, 2016, 44(11): 1655-1661.
32	俞志敏, 卫新来, 娄梅生, 等. 氯化锌活化生物质炭制备活性炭及其表征[J]. 化工进展, 2014, 33(12): 3318-3323.
	YU Z M, WEI X L, LOU M S, et al. Preparation and characterization of activated carbon from bio-char by chemical activation with ZnCl₂[J]. Chemical Industry and Engineering Progress, 2014, 33(12): 3318-3323.
33	LEE D, LEE B, PARK K H, et al. Scalable exfoliation process for highly soluble boron nitride nanoplatelets by hydroxide-assisted ball milling[J]. Nano Letters, 2015, 15(2): 1238-1244.
34	THIRUMAL V, PANDURANGAN A, JAYAVEL R, et al. Synthesis and characterization of boron doped graphene nanosheets for supercapacitor applications[J]. Synthetic Metals, 2016, 220: 524-532.
35	张凯, 韦秀丽, 王冰, 等. Fe₃O₄改性水热炭活化过硫酸钠降解罗丹明B[J]. 化工进展, 2020, 39(7): 2867-2875.
	ZHANG K, WEI X L, WANG B, et al. Degradation of Rhodamine B by sodium persulfate activated with Fe₃O₄ modified hydrochar[J]. Chemical Industry and Engineering Progress, 2020, 39(7): 2867-2875.
36	ZHOU H, WU S K, ZHOU Y Y, et al. Insights into the oxidation of organic contaminants by iron nanoparticles encapsulated within boron and nitrogen co-doped carbon nanoshell: catalyzed Fenton-like reaction at natural pH[J]. Environment International, 2019, 128: 77-88.
37	LIANG H W, WEI W, WU Z S, et al. Mesoporous metal-nitrogen-doped carbon electrocatalysts for highly efficient oxygen reduction reaction[J]. Journal of the American Chemical Society, 2013, 135(43): 16002-16005.
38	ZHENG Y, JIAO Y, GE L, et al. Two-step boron and nitrogen doping in graphene for enhanced synergistic catalysis[J]. Angewandte Chemie International Edition, 2013, 52(11): 3110-3116.
39	CHEN S C, CHEN Z H, SIAHROSTAMI S, et al. Designing boron nitride islands in carbon materials for efficient electrochemical synthesis of hydrogen peroxide[J]. Journal of the American Chemical Society, 2018, 140(25): 7851-7859.
40	LAN H C, LI J F, SUN M, et al. Efficient conversion of dimethylarsinate into arsenic and its simultaneous adsorption removal over FeC_x/N-doped carbon fiber composite in an electro-Fenton process [J]. Water Research, 2016, 100: 57-64.
41	SUN Y Y, SINEV I, JU W, et al. Efficient electrochemical hydrogen peroxide production from molecular oxygen on nitrogen-doped mesoporous carbon catalysts[J]. ACS Catalysis, 2018, 8(4): 2844-2856.
42	HUANG T Z, MAO S, QIU M, et al. Nitrogen-boron dipolar-doped nanocarbon as a high-efficiency electrocatalyst for oxygen reduction reaction[J]. Electrochimica Acta, 2016, 222: 481-487.
43	SU P, ZHOU M H, REN G B, et al. A carbon nanotube-confined iron modified cathode with prominent stability and activity for heterogeneous electro-Fenton reactions[J]. Journal of Materials Chemistry A, 2019, 7(42): 24408-24419.
44	DONG P, LIU W J, WANG S J, et al. In suit synthesis of Fe₃O₄ on carbon fiber paper@polyaniline substrate as novel self-supported electrode for heterogeneous electro-Fenton oxidation[J]. Electrochimica Acta, 2019, 308: 54-63.
45	YANG W L, ZHOU M H, LIANG L. Highly efficient in-situ metal-free electrochemical advanced oxidation process using graphite felt modified with N-doped graphene[J]. Chemical Engineering Journal, 2018, 338: 700-708.

样品	电子转移数n
样品	-0.60V	-0.70V	-0.80V	-0.90V	-1.00V
N/B/Fe@BC	1.88	1.87	1.87	1.96	2.23
Fe@BC	2.26	2.35	2.53	2.85	3.72
N/B@BC	2.23	2.12	2.10	2.26	2.95
BC	2.10	2.13	2.22	2.49	3.38

样品	电子转移数n
样品	-0.60V	-0.70V	-0.80V	-0.90V	-1.00V
N/B/Fe@BC	1.88	1.87	1.87	1.96	2.23
Fe@BC	2.26	2.35	2.53	2.85	3.72
N/B@BC	2.23	2.12	2.10	2.26	2.95
BC	2.10	2.13	2.22	2.49	3.38

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