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

doi:10.11949/0438-1157.20200311

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5628-5635.DOI: 10.11949/0438-1157.20200311

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

陈功³(),武煜翔³,卢真保²,王炳锋⁴,杨东晓³,赵钟兴^1,³(),黄艳²()

^1.华宝香精股份有限公司，西藏拉萨 850000
^2.广州华芳烟用香精有限公司，广东广州 510530
^3.广西大学化学化工学院，广西南宁 530004
^4.华南农业大学材料与能源学院，广东广州 510642

收稿日期:2020-03-24 修回日期:2020-06-05 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 赵钟兴,黄艳
作者简介:陈功（1996—），男，硕士研究生，844649803@qq.com
基金资助:
国家自然科学基金项目(21666004);广西高校大学生创新创业训练计划项目(201910593044)

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

CHEN Gong³(),WU Yuxiang³,LU Zhenbao²,WANG Bingfeng⁴,YANG Dongxiao³,ZHAO Zhongxing^1,³(),HUANG Yan²()

^1.Huabao Flavor Company Limited by Shares, Lhasa 850000, Tibet, China
^2.Guangzhou Huafang Tobacco Flavor Company Limited by Shares, Guangzhou 510530, Guangdong, China
^3.School of Chemistry ＆ Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^4.College of Materials and Energy, South China Agricultural University, Guangzhou 510642, Guangdong, China

Received:2020-03-24 Revised:2020-06-05 Online:2020-12-05 Published:2020-12-05
Contact: ZHAO Zhongxing,HUANG Yan

摘要/Abstract

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

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

中图分类号:

TQ 656.5

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.

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.

图/表 10

图1 Fe/Z-ASE 的SEM和EDS元素分布图

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

图2 Fe/Z-ASE材料的XRD谱图

Fig.2 XRD pattern of Fe/Z-ASE

图3 Fe/Z-ASE材料的N2吸附-脱附等温线和DFT孔径分布

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

表1 Fe/Z-ASE的孔结构参数

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

图4 苯乙醇和茴香醚蒸气在Fe/Z-ASE材料上的吸附动力学

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

图5 在Fe/Z-ASE材料上不同苯乙醇和茴香醚吸附量对应脱附保留率的关系

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

图6 在Fe/Z-ASE上不同吸附量苯乙醇和茴香醚的释放速率曲线

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

图7 苯乙醇和茴香醚的前线轨道分布示意图

Fig.7 Population of frontier orbitals for pheneylethanol and anisole

表2 苯乙醇和茴香醚的绝对硬度和电负性

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

图8 苯乙醇分子动力学示意图

Fig.8 Molecular dynamics sketch of pheneylethanol

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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

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

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