木质素制备燃料电池阴极电催化炭材料研究(Ⅳ)——材料的制备及其催化氧气还原性能

doi:10.3969/j.issn.0253-2417.2021.06.004

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (6): 27-35.doi: 10.3969/j.issn.0253-2417.2021.06.004

木质素制备燃料电池阴极电催化炭材料研究(Ⅳ)——材料的制备及其催化氧气还原性能

金凯楠¹, 左宋林¹^,*(), 桂有才¹, 申保收²^,³^,*(), 王珊珊¹, 崔难难¹

1. 南京林业大学化学工程学院, 江苏南京 210037
2. 陕西省地表系统与环境承载力重点实验室, 陕西西安 710127
3. 西北大学城市与环境学院/地表系统与灾害研究院, 陕西西安 710127

收稿日期:2021-07-14 出版日期:2021-12-28 发布日期:2021-12-31
通讯作者: 左宋林,申保收 E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn
作者简介:申保收, 副教授, 硕士生导师, 研究领域为环境及储能材料与环境水化学, E-mail: bsshen@nwu.edu.cn
左宋林, 教授, 博士生导师, 研究领域为生物质热化学转化与炭材料, E-mail: zslnl@njfu.edu.cn
金凯楠(1996-), 男, 江苏南京人, 硕士生, 从事木质素的改性与应用研究
基金资助:
国家重点研发计划资助项目(2019YFB1503804);江苏省自然科学基金青年项目(BK20170928)

Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅳ: Preparation and Electrocatalytic Properties for Oxygen Reduction Reaction

Kainan JIN¹, Songlin ZUO¹^,*(), Youcai GUI¹, Baoshou SHEN²^,³^,*(), Shanshan WANG¹, Nannan CUI¹

1. College of Chemical Engineering, Nanjing Forestry University, Nanjing 210037, China
2. Shaanxi Key Laboratory of Earth Surface System and Environmental Carrying Capacity, Xi'an 710127, China
3. College of Urban and Environmental Sciences/Institute of Earth Surface System and Hazards, Northwest University, Xi'an 710127, China

Received:2021-07-14 Online:2021-12-28 Published:2021-12-31
Contact: Songlin ZUO,Baoshou SHEN E-mail:zslnl@njfu.edu.cn;bsshen@nwu.edu.cn

摘要/Abstract

摘要：

在对酶解木质素以及尿素、三聚氰胺改性木质素的热解过程、木质素基炭的化学结构和微观结构等系列研究基础上，采用木质素改性、炭化和氨气活化等过程制备了木质素基活性炭，运用氮气吸附法、傅里叶变换红外光谱、X射线光电子能谱和电化学等方法分析了木质素基活性炭的孔隙结构、表面化学结构与电催化氧气还原反应（ORR）的催化性能。研究结果表明：以酶解木质素为原料，通过含氮化合物改性、炭化和高温氨气活化能够制备出ORR电催化性能优良的木质素基活性炭。采用含氮化合物改性和氨气活化的方法，可以有效调控木质素基活性炭的孔隙结构，以及吡啶氮（N-6）、吡咯氮（N-5）和季氮（N-Q）等含氮基团含量，从而达到调控木质素基活性炭的ORR电催化性能的目的。木质素经三聚氰胺改性、800 ℃炭化、950 ℃氨气活化制得的活性炭L-M-800-NH₃-950比表面积为1 304 m²/g，微孔（0.438 cm³/g）和中孔（0.302 cm³/g）结构发达，含氮量为6.82%，季氮基团为64.8%，电催化性能与商业20% Pt/C材料接近。

关键词: 木质素, 活性炭, 电催化, 氧气还原, 三聚氰胺

Abstract:

Lignin-based activated carbons were prepared by the consecutive procedure of lignin modification, carbonization and ammonia activation using enzymatic hydrolysis lignin as starting material, in terms of our serial investigations that have been conducted on pyrolysis of starting materials, surface chemistry and microstructure of lignin-derived chars. Nitrogen adsorption, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy and electronic chemistry methods were employed to characterize the pore structure and surface chemistry of lignin-based activated carbons and to evaluate the catalytic performance as electrocatalysts for oxygen reduction reaction(ORR). The results showed that lignin-based activated carbons with good performance of electronically catalyzing ORR could be obtained through nitrogen-containing chemicals modification of enzymatic hydrolysis lignin followed by carbonization and ammonia activation. By combing the method of lignin modification with nitrogen-containing substances and ammonia activation, the pore structure and the concentration of nitrogen-containing groups including pyridine-like, pyrrole-like and quaternary-like species could be tuned and, as a result, benefit to regulate the electrocatalytic properties of lignin-based activated carbons. Using melamine-modified enzymatic hydrolysis lignin as starting material produced the lignin-based activated carbons with a comparable electrocatalytic performance with commercially available 20% Pt/C catalyst, which possess a surface areas of more than 1 300 m²/g, developed microporosity and mesoporisty, a nitrogen content of more than 6% and a high concentration of quaternary-like groups.

Key words: lignin, activated carbon, electrocatalysis, oxygen reduction reaction, melamine

中图分类号:

TQ35

金凯楠, 左宋林, 桂有才, 申保收, 王珊珊, 崔难难. 木质素制备燃料电池阴极电催化炭材料研究(Ⅳ)——材料的制备及其催化氧气还原性能[J]. 林产化学与工业, 2021, 41(6): 27-35.

Kainan JIN, Songlin ZUO, Youcai GUI, Baoshou SHEN, Shanshan WANG, Nannan CUI. Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅳ: Preparation and Electrocatalytic Properties for Oxygen Reduction Reaction[J]. Chemistry and Industry of Forest Products, 2021, 41(6): 27-35.

图/表 8

图1

表1

表2

图2

表3

图3

表4

图4

参考文献 22

1	GONG K P , DU F , XIA Z H , et al. Nitrogen-doped carbon nanotube arrays with high electrocatalytic activity for oxygen reduction[J]. Science, 2009, 323 (5915): 760- 764. doi: 10.1126/science.1168049
2	ZHAO Y , NAKAMURA R , KAMIYA K , et al. Nitrogen-doped carbon nanomaterials as non-metal electrocatalysts for water oxidation[J]. Nature Communications, 2013, 4, 1- 7.
3	BORGHEI M , LAOCHAROEN N , PÕLDSEPP E K , et al. Porous N, P-doped carbon from coconut shells with high electrocatalytic activity for oxygen reduction: Alternative to Pt-C for alkaline fuel cells[J]. Applied Catalysis B: Environmental, 2017, 204, 394- 402. doi: 10.1016/j.apcatb.2016.11.029
4	WANG Y F , ZUO S L , LIU Y . Ammoniamodification of high-surface-area activated carbons as metal-free electrocatalysts for oxygen reduction reaction[J]. Electrochimica Acta, 2018, 263, 465- 473. doi: 10.1016/j.electacta.2018.01.089
5	WANG K L , XU M , GU Y , et al. Symmetric supercapacitors using urea-modified lignin derived N-doped porous carbon as electrode materials in liquid and solid electrolytes[J]. Journal of Power Sources, 2016, 332, 180- 186. doi: 10.1016/j.jpowsour.2016.09.115
6	ZHANG L M , YOU T T , ZHOU T , et al. Interconnected hierarchical porous carbon from lignin-derived byproducts of bioethanol production for ultra-high performance supercapacitors[J]. ACS Applied Materials & Interfaces, 2016, 8 (22): 13918- 13925.
7	ZHAO H J , WANG Q J , DENG Y H , et al. Preparation of renewable lignin-derived nitrogen-doped carbon nanospheres as anodes for lithium-ion batteries[J]. RSC Advances, 2016, 6 (81): 77143- 77150. doi: 10.1039/C6RA17793J
8	DU L L , WU W , LUO C . Lignin-derived nitrogen-doped porous carbon as a high-rate anode material for sodium ion batteries[J]. Journal of the Electrochemical Society, 2019, 166 (2): A423- A428. doi: 10.1149/2.1361902jes
9	ZHANG X L , YU D L , ZHANG Y Q , et al. Nitrogen-and sulfur-doped carbon nanoplatelets via thermal annealing of alkaline lignin with urea as efficient electrocatalysts for oxygen reduction reaction[J]. RSC Advances, 2016, 6 (106): 104183- 104192. doi: 10.1039/C6RA21958F
10	ZHANG M L , SONG Y L , TAO H C , et al. Lignosulfonate biomass derived N and S co-doped porous carbon for efficient oxygen reduction reaction[J]. Sustainable Energy & Fuels, 2018, 2 (8): 1820- 1827.
11	GRAGLIA M , PAMPEL J , HANTKE T , et al. Nitro lignin-derived nitrogen-doped carbon as an efficient and sustainable electrocatalyst for oxygen reduction[J]. ACS Nano, 2016, 10 (4): 4364- 4371. doi: 10.1021/acsnano.5b08040
12	SHEN Y X , PENG F , CAO Y H , et al. Preparation of nitrogen and sulfur co-doped ultrathin graphitic carbon via annealing bagasse lignin as potential electrocatalyst towards oxygen reduction reaction in alkaline and acid media[J]. Journal of Energy Chemistry, 2019, 34, 33- 42. doi: 10.1016/j.jechem.2018.09.021
13	XIONG D B, LI X F, FAN L L, et al. Three-dimensional heteroatom-doped nanocarbon for metal-free oxygen reduction electrocatalysis: A review[J/OL]. Catalysts, 2018, 8(8): 1-23[2021-05-25]. https://doi:10.3390/catal8080301.
14	ZUO S L , ZHANG W B , WANG Y F , et al. Low-cost preparation of high-surface-area nitrogen-containing activated carbons from biomass-based chars by ammonia activation[J]. Industrial & Engineering Chemistry Research, 2020, 59 (16): 7527- 7537.
15	陈继锡, 左宋林, 王永芳, 等. 磷酸法活性炭的三聚氰胺表面改性及其电化学性能研究[J]. 林产化学与工业, 2016, 36 (2): 37- 44. doi: 10.3969/j.issn.0253-2417.2016.02.006
	CHEN J X , ZUO S L , WANG Y F , et al. Electrochemical properties of phosphoric acid activated carbon modified by melamine[J]. Chemistry and Industry of Forest Products, 2016, 36 (2): 37- 44. doi: 10.3969/j.issn.0253-2417.2016.02.006
16	张文彬, 左宋林, 王宜望. 氨气改性活性炭表面含氮官能团的形成与演变[J]. 林产化学与工业, 2017, 37 (2): 35- 41.
	ZHANG W B , ZUO S L , WANG Y W . Formation and evolution of surface nitrogen functionalities on activated carbons by ammonia modification[J]. Chemistry and Industry of Forest Products, 2017, 37 (2): 35- 41.
17	DEMIR M , FARGHALY A A , DECUIR M J , et al. Supercapacitance and oxygen reduction characteristics of sulfur self-doped micro/mesoporous bio-carbon derived from lignin[J]. Materials Chemistry and Physics, 2018, 216, 508- 516. doi: 10.1016/j.matchemphys.2018.06.008
18	PANDIAN B, ARUNACHALAM R, EASWARAMOORTHI S, et al. Tuning of renewable biomass lignin into high value-added product: Development of light resistant azo-lignin colorant for coating application[J/OL]. Journal of Cleaner Production, 2020, 256: 1-10[2021-05-25]. https://doi:10.1016/j.jclepro.2020.120455.
19	XU L J , YAO Q , ZHANG Y , et al. Integrated production of aromatic amines and N-doped carbon from lignin via ex situ catalytic fast pyrolysis in the presence of ammonia over zeolites[J]. ACS Sustainable Chemistry & Engineering, 2017, 5 (4): 2960- 2969.
20	HAN J , ZHANG L , ZHAO B , et al. The N-doped activated carbon derived from sugarcane bagasse for CO₂ adsorption[J]. Industrial Crops & Products, 2019, 128, 290- 297.
21	RATSO S , KRUUSENBERG I , VIKKISK M , et al. Highly active nitrogen-doped few-layer graphene/carbon nanotube composite electrocatalyst for oxygen reduction reaction in alkaline media[J]. Carbon, 2014, 73, 361- 370. doi: 10.1016/j.carbon.2014.02.076
22	LAI L F , POTTS J R , ZHAN D , et al. Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction[J]. Energy & Environmental Science, 2012, 5, 7936- 7942.

样品sample	S_BET/(m²·g^-1)	V_tot/(cm³·g^-1)	V_mic/(cm³·g^-1)	V_mes/(cm³·g^-1)
L-800-950	44	0.056	0.013	0.043
L-U-800-950	34	0.052	0.004	0.048
L-M-800-950	72	0.091	0.005	0.086
L-800-NH₃-950	1373	0.730	0.474	0.255
L-U-800-NH₃-950	1324	0.738	0.470	0.268
L-M-800-NH₃-950	1304	0.740	0.438	0.302

样品 sample	得率/% yield	元素质量分数element mass fraction/%
样品 sample	得率/% yield	C	H	N
L-800-950	29.1	97.26	0.27	0.76
L-U-800-950	19.3	94.21	0.4	3.17
L-M-800-950	24.7	93.12	0.5	5.77
L-800-NH₃-950	12.4	94.36	0.32	4.96
L-U-800-NH₃-950	8.7	94.55	0.35	4.69
L-M-800-NH₃-950	7.5	93.86	0.04	6.82

样品 sample	N1s/%
样品 sample	N-6	N-5	N-Q	N-X
L-U-800-950	29.9	8.6	58.4	3.1
L-M-800-950	41.8	3.7	54.5	0.0
L-800-NH₃-950	44.9	15.3	39.7	0.0
L-U-800-NH₃-950	31.4	6.9	58.3	3.4
L-M-800-NH₃-950	27.4	7.8	64.8	0.0

样品sample	E_O/V	E_1/2/V	J/(mA·cm^-2)
20% Pt/C	-0.171	-0.306	-5.03
L-800-950	-0.430	-0.587	-2.39
L-U-800-950	-0.418	-0.584	-2.38
L-M-800-950	-0.427	-0.599	-2.67
L-800-NH₃-950	-0.218	-0.409	-3.18
L-U-800-NH₃-950	-0.204	-0.401	-3.53
L-M-800-NH₃-950	-0.178	-0.369	-4.71

[1]	金凯楠, 左宋林, 桂有才, 申保收. 木质素制备燃料电池阴极电催化炭材料研究(Ⅰ)——改性酶解木质素的热解过程[J]. 林产化学与工业, 2021, 41(6): 1-9.
[2]	金凯楠, 左宋林, 桂有才, 申保收, 王珊珊, 胡欣. 木质素制备燃料电池阴极电催化炭材料研究(Ⅱ)——改性酶解木质素炭的化学结构演变[J]. 林产化学与工业, 2021, 41(6): 10-18.
[3]	左宋林, 金凯楠, 桂有才, 申保收, 王珊珊, 杨梦梅. 木质素制备燃料电池阴极电催化炭材料研究(Ⅲ)——改性酶解木质素炭的微观结构演变[J]. 林产化学与工业, 2021, 41(6): 19-26.
[4]	侯兴隆, 建晓朋, 许伟, 郭奇, 刘军利. 基于TG-FTIR-MS技术的酶解木质素热解行为分析[J]. 林产化学与工业, 2021, 41(6): 36-42.
[5]	罗路, 罗凌聪, 邓剑平, 陈婷婷, 范毜仔, 杜官本, 赵伟刚. 硼/氮共掺杂刀豆壳基多孔炭材料的制备及其电化学性能研究[J]. 林产化学与工业, 2021, 41(6): 43-50.
[6]	建晓朋, 侯兴隆, 许伟, 刘石彩. 活性炭孔结构对CS₂吸附/脱附性能的影响[J]. 林产化学与工业, 2021, 41(6): 90-96.
[7]	田杰, 娄瑞, 薛香玉, 张宏, 武书彬, 许慧敏. 纳米木质素的热解特性及其反应动力学分析[J]. 林产化学与工业, 2021, 41(6): 97-104.
[8]	马悦, 李旭, 刘志明. 木质素磺酸钠基膨胀阻燃聚氨酯泡沫的制备及性能[J]. 林产化学与工业, 2021, 41(5): 31-37.
[9]	韩有奇, 倪佳馨, 黄晓琳, 李煜东, 姜贵全, 韩世岩. CQDs/TiO₂的制备及光催化性能[J]. 林产化学与工业, 2021, 41(5): 58-64.
[10]	陈浩男, 于婷, 周亚丽, 雷西萍, 关晓琳. 生物质活性炭基超级电容器电极材料研究进展[J]. 林产化学与工业, 2021, 41(5): 113-125.
[11]	梁孟珂, 陈静, 戴鹏, 马晓峰, 张猛, 罗振扬. 木质素基膨胀型阻燃剂的制备及其应用[J]. 林产化学与工业, 2021, 41(4): 10-16.
[12]	王琼, 杨旋, 蔡政汉, 陈燕丹, 黄彪, 林冠烽. 基于碱/硫脲协同活化制备多元掺杂活性炭[J]. 林产化学与工业, 2021, 41(4): 77-84.
[13]	金灿, 刘云龙, 霍淑平, 吴国民, 刘贵锋, 孔振武. 木质素基多孔炭材料及其在水体净化中的应用研究进展[J]. 林产化学与工业, 2021, 41(4): 111-123.
[14]	李梦竹, 王霆. 抑制木质素降解中间体再聚合的研究进展[J]. 林产化学与工业, 2021, 41(4): 124-134.
[15]	李卓, 翁述贤, 宋飞, 任晓丽, 杨晓慧, 胡立红. 木质素基含氮磷阻燃剂的合成及热重分析[J]. 林产化学与工业, 2021, 41(3): 63-70.

木质素制备燃料电池阴极电催化炭材料研究(Ⅳ)——材料的制备及其催化氧气还原性能

Studies on Lignin-based Carbon Materials as Electrocatalysts of Fuel Cells Cathode Ⅳ: Preparation and Electrocatalytic Properties for Oxygen Reduction Reaction

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 8

参考文献 22

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们