Storage and release properties of pheneylethanol and anisole flavor on Fe-based silkworm excrement biocarbon

doi:10.11949/0438-1157.20200311

Abstract

Abstract:

The silkworm waste from the silkworm was selected as the carbon source, and ZnCl₂ and FeCl₂ were used as activators to obtain a Fe-doped highly graphitized porous biochar material Fe/Z-ASE through a one-step synthesis method. The fabricated Fe/Z-ASE was tested for the adsorption and sustained-release kinetics of pheneylethanol and anisole while their mutual interaction and intermolecular interactions were evaluated by quantum chemical calculation. The silkworm feces exhibited a well-developed pore structure, high surface graphitized carbon content, high BET surface area (950.9 m²/g), more than 60% mesopores and uniform distribution of Fe. Fe/Z-ASE exhibited hydrophobic surface and weak polarity, while anisole realized higher adsorption capacity (510 mg/g) and diffusion rate of 1.7×10^-2 min^-1 than that of phenylethanol under variable anisole adsorption amounts (150—510 mg/g). Density functional simulations suggested anisole and phenylethanol as weak bases and hence interacted with the weakly acidic adsorption sites (Fe-C) on the Fe/Z-ASE, while the relatively higher basicity of anisole endorsed it stronger interaction with Fe/Z-ASE. Molecular dynamics analysis showed strong hydrogen bonding between pheneylethanol molecules while no such interaction existed among anisole molecules, which hindered the desorption of pheneylethanol molecules under high initial adsorption capacity as compared to those of anisole.

Key words: Fe-based silkworm excrement biocarbon, adsorption, desorption, pheneylethanol, anisole, molecular simulation

摘要：

选用桑蚕废弃物蚕沙为碳源，利用ZnCl₂和FeCl₂作为活化剂，通过一步合成法获得一种Fe掺杂高石墨化多孔生物炭材料Fe/Z-ASE，并测定香精化合物分子苯乙醇和茴香醚在Fe/Z-ASE上的吸附和缓释动力学行为，然后再通过量子化学计算分析苯乙醇、茴香醚与Fe/Z-ASE的作用关系以及苯乙醇、茴香醚分子间作用力。结果发现：蚕沙多孔炭Fe/Z-ASE孔隙结构发达，表面石墨化碳含量高，Fe元素分布均匀，其BET比表面积为950.9 m²/g且中孔占60%以上，是一种表面疏水并呈现弱极性的多级孔生物炭材料；在苯乙醇和茴香醚的扩散和控释过程中，茴香醚具有比苯乙醇更高的吸附量（510 mg/g）和扩散动力学常数（1.7×10^-2 min^-1），而且在不同初始茴香醚吸附量下（150~500 mg/g）其都能获得较好的控释效果。随后通过密度泛函DFT模拟计算可知，茴香醚和苯乙醇都是弱碱，能与Fe/Z-ASE材料上的弱酸性吸附位（Fe-C）产生相互作用，而且由于茴香醚的碱性更弱，所以与Fe/Z-ASE的作用力更强。然后再通过分子动力学分析可知，苯乙醇分子间能产生强氢键作用而茴香醚分子间不存在强相互作用，所以苯乙醇分子在高初始吸附量下不易被脱附，而茴香醚分子在高/低初始吸附量下都能获得较高脱附保留率。

关键词: Fe基蚕沙生物炭, 吸附, 脱附, 苯乙醇, 茴香醚, 分子模拟

CLC Number:

TQ 656.5

CHEN Gong,WU Yuxiang,LU Zhenbao,WANG Bingfeng,YANG Dongxiao,ZHAO Zhongxing,HUANG Yan. Storage and release properties of pheneylethanol and anisole flavor on Fe-based silkworm excrement biocarbon[J]. CIESC Journal, 2020, 71(12): 5628-5635.

陈功,武煜翔,卢真保,王炳锋,杨东晓,赵钟兴,黄艳. 苯乙醇和茴香醚在含Fe蚕沙基生物碳材料的储香与释放性能研究[J]. 化工学报, 2020, 71(12): 5628-5635.

Figures/Tables 10

Fig.1 SEM and EDS of Fe/Z-ASE

Fig.2 XRD pattern of Fe/Z-ASE

Fig.3 N2 adsorption-desorption isotherms and DFT pore-size distribution of Fe/Z-ASE

Table 1 Pore textural parameters of Fe/Z-ASE

Sample	S_BET/(m²/g)	S_mic/(m²/g)	S_meso/(m²/g)	S_meso/ S_mic	V_mic/(cm³/g)	V_total/(cm³/g)	Pore size/?
Fe/Z-ASE	950.9	347.5	603.4	1.7	0.07	0.92	6.7—34.1

Fig.4 Adsorption kinetics curves of vapor pheneylethanol and anisole flavors on Fe/Z-ASE

Fig.5 Effect of adsorption capacity of pheneylethanol and anisole on Fe/Z-ASE on their release rate

Fig.6 Release rate of low and high initial adsorption amounts of pheneylethanol and anisole on Fe/Z-ASE materials

Fig.7 Population of frontier orbitals for pheneylethanol and anisole

Table 2 Absolute hardness and electron affinity of pheneylethanol and anisole

Molecule	E_LUMO / eV	E_HOMO / eV	η / eV	χ / eV
pheneylethanol	-0.240	0.00169	0.121	0.119
anisole	-0.216	0.00311	0.109	0.106

Fig.8 Molecular dynamics sketch of pheneylethanol

References 31

1	Ayseli M T, Ayseli Y İ. Flavors of the future: health benefits of flavor precursors and volatile compounds in plant foods[J]. Trends in Food Science & Technology, 2016, 26(48): 69-77.
2	姚瑞雄. 我国香精香料工业的现状与分析[J]. 食品安全导刊, 2017, 12(18): 121-122.
	Yao R X. Status and analysis of flavor and fragrance industry in China[J]. China Food Safety Magazine, 2017, 12(18): 121-122.
3	王璐, 毛海涛, 张磊, 等. 基于反向机器学习的调香设计方法[J]. 化工学报, 2019, 70(12): 4722-4729.
	Wang L, Mao H T, Zhang L, et al. Inverse machine learning-based fragrance tuned design method[J]. CIESC Journal, 2019, 70(12): 4722-4729.
4	高海有, 刘秀明, 高莉, 等. 烟用香精香料研究现状与发展趋势[J]. 香料香精化妆品, 2019, 4(2): 70-73.
	Gao H Y, Liu X M, Gao L, et al. The current situation and trends of tobacco flavor research [J]. Flavour Fragrance Cosmetics, 2019, 4 (2): 70-73.
5	Qian Y, Yuan Y, Wang H, et al. Highly efficient uranium adsorption by salicylaldoxime/polydopamine graphene oxide nanocomposites[J]. Journal of Materials Chemistry A, 2018, 6(48): 24676-24685.
6	Chai K, Lu K, Xu Z, et al. Rapid and selective recovery of acetophenone from petrochemical effluents by crosslinked starch polymer[J]. Journal of Hazardous Materials, 2018, 348: 20-28.
7	李龙, 葛天舒, 吴宣楠, 等. 硅胶嵌入多孔纸基对苯蒸气吸附性能[J]. 化工学报, 2019, 70(3): 951-959.
	Li L, Ge T S, Wu X N, et al. Adsorption properties of paper based silica gel adsorbents for benzene vapor[J]. CIESC Journal, 2019, 70 (3): 951-959.
8	Chen Y, Yu B, Lin J, et al. Simultaneous adsorption and biodegradation (SAB) of diesel oil using immobilized Acinetobacter venetianus on porous material[J]. Chemical Engineering Journal, 2016, 19(289): 463-470.
9	Sun J, Li Q, Luo S, et al. Characterization of key aroma compounds in meilanchun sesame flavor style Baijiu by application of aroma extract dilution analysis, quantitative measurements, aroma recombination, and omission/addition experiments[J]. RSC Advances, 2018, 8(42): 23757-23767.
10	Hou C, Wang J, Du W, et al. One-pot synthesized molybdenum dioxide-molybdenum carbide heterostructures coupled with 3D holey carbon nanosheets for highly efficient and ultrastable cycling lithium-ion storage [J]. Journal of Materials Chemistry A, 2019, 7(22): 13460-13472.
11	Zhang M, Meng J, Liu Q, et al. Corn stover-derived biochar for efficient adsorption of oxytetracycline from wastewater[J]. Journal of Materials Research, 2019, 34(17): 1-11.
12	Tao M, Sun H, Liu L, et al. Graphitized porous carbon for rapid screening of angiotensin-converting enzyme inhibitory peptide GAMVVH from silkworm pupa protein and molecular insight into inhibition mechanism[J]. Journal of Agricultural and Food Chemistry, 2017, 65(39): 8626-8633.
13	王丽, 王兴杰, 李浩, 等. 葡萄糖基多孔碳材料对CO2/CH4的分离性能[J]. 化工学报, 2018, 69(2): 733-740.
	Wang L, Wang X J, Li H, et al. Separation performance of CO2/CH4 on porous carbons derived from glucose[J]. CIESC Journal, 2018, 69 (2): 733-740.
14	黄奕瑕. 新型多孔固体卷烟2-环戊烯酮缓释材料研制[D]. 广州: 华南理工大学, 2015.
	Huang Y X. Research on novel porous solid slow-release materials of 2-cyclopentenone[D]. Guangzhou: South China University of Technology, 2015.
15	王明锋, 熊智勇, 刘娟, 等. β-苯乙醇在不同类型多孔材料上的脱附活化能[J]. 中国烟草学报, 2014, 20(2): 34-38.
	Wang M F, Xiong Z Y, Liu J, et al. Desorption activation energy of β-phenylethyl alcohol on different type of porous materials[J]. Acta Tabacaria Sinica, 2014, 20(2): 34-38.
16	Zhu M, Zhou K, Sun X, et al. Hydrophobic N-doped porous biocarbon from dopamine for high selective adsorption of p-xylene under humid conditions[J]. Chemical Engineering Journal, 2017, 20(317): 660-672.
17	张智, 马修卫, 李津津, 等. 中高温环境下VOCs在活性炭上的吸附性能研究[J]. 化工学报, 2019, 70(12): 4811-4820.
	Zhang Z, Ma X W, Li J J, et al. Study on adsorption capacity of VOCs on activated carbon at medium-high temperature[J]. CIESC Journal, 2019, 70(12): 4811-4820.
18	周枫, 李智宇, 李根, 等. 茴香醚在葡萄糖基多孔碳材料上缓释机理[J]. 化工学报, 2017, 68(12): 4625-4632.
	Zhou F, Li Z Y, Li G, et al. Release-slowing mechanism of anisole on glucose-based porous carbon materials[J]. CIESC Journal, 2017, 68(12): 4625-4632.
19	Marinescu M, Tudorache D G, Marton G I, et al. Density functional theory molecular modeling, chemical synthesis, and antimicrobial behaviour of selected benzimidazole derivatives[J]. Journal of Molecular Structure, 2017, 1130: 463-471.
20	Mines P D, Thirion D, Uthuppu B, et al. Covalent organic polymer functionalization of activated carbon surfaces through acyl chloride for environmental clean-up[J]. Chemical Engineering Journal, 2017, 20(309): 766-771.
21	Kitajou A, Kudo S, Hayashi J, et al. Synthesis and electrochemical properties of Fe3C-carbon composite as an anode material for lithium-ion batteries[J]. Electrochemistry, 2017, 85(10): 630-633.
22	Wang Q, Zhang W, Guo C, et al. In situ construction of 3D interconnected FeS@Fe3C@graphitic carbon networks for high-performance sodium-ion batteries[J]. Advanced Functional Materials, 2017, 27(41): 1703390.
23	陈岚, 权宇珩, 李志勇, 等. 超声波辅助粉煤灰去除水中亚甲基蓝染料的动力学分析[J]. 化工学报, 2019, 70(7): 2708-2716.
	Chen L, Quan Y H, Li Z Y, et al. Kinetic analysis of removal of methylene blue using fly ash assisted by ultrasound from aqueous solution[J]. CIESC Journal, 2019, 70 (7): 2708-2716.
24	Ling C, Xue Q, Jing N, et al. Effect of functional groups on the radial collapse and elasticity of carbon nanotubes under hydrostatic pressure[J]. Nanoscale, 2012, 4(13): 3894-3900.
25	Tang J, Qu S, Hu J, et al. A new organic dye bearing aldehyde electron-withdrawing group for dye-sensitized solar cell[J]. Solar Energy, 2012, 86(9): 2306-2311.
26	Álvarez-Torrellas S, Ribeiro R S, Gomes H T, et al. Removal of antibiotic compounds by adsorption using glycerol-based carbon materials[J]. Chemical Engineering Journal, 2016, 19(296): 277-288.
27	Hu Q, Nan C, Feng C, et al. Kinetic and isotherm studies of nitrate adsorption on granular Fe-Zr-chitosan complex and electrochemical reduction of nitrate from the spent regenerant solution[J]. RSC Advances, 2016, 6(66): 61944-61954.
28	王颖, 张亮, 吕乔, 等. 活性炭对茉莉香精的吸附及缓释性能研究[J]. 轻工科技, 2015, 31(11): 41-42.
	Wang Y, Zhang L, Lyu Q, et al. Study on the adsorption and slow-release properties of jasmine flavor by activated carbon[J]. Light Industry Science and Technology, 2015, 31(11): 41-42.
29	武煜翔, 王欣辉, 柴坤刚, 等. 蚕沙基多孔炭表面氧化改性对农药噻虫嗪吸附及缓控释影响[J]. 化工学报, 2018, 69(6): 2797-2804.
	Wu Y X, Wang X H, Chai K G, et al. Oxidized modification of novel silkworm excrement-based porous biocarbon with various acids for sustained release of pesticide thiamethoxam[J]. CIESC Journal, 2018, 69(6): 2797-2804.
30	Wei Y, Wu Y, Chang Q, et al. Ultrasonic-assisted modification of a novel silkworm-excrement-based porous carbon with various Lewis acid metal ions for the sustained release of the pesticide thiamethoxam[J]. RSC Advances, 2017, 7(48): 30020-30031.
31	魏君怡, 李勇, 薛向欣. 基于离子液体的“可设计性”和“软酸”性质萃取分离电镀污泥中Cr6+/Fe3+[J]. 化工学报, 2017, 68(9): 3451-3458.
	Wei J Y, Li Y, Xue X X. Cr6+/Fe3+ extraction separation from electroplating sludge based on designability and soft acidity of ionic liquids[J]. CIESC Journal, 2017, 68 (9): 3451-3458.

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