氮化硼纳米片吸附Cd(II)的动力学和热力学研究

doi:10.15541/jim20190371

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 284-292.DOI: 10.15541/jim20190371

所属专题： 2020年环境材料论文精选(二)重金属元素去除

氮化硼纳米片吸附Cd(II)的动力学和热力学研究

李丽¹,郭筱洁²,金阳¹,陈朝贵¹(),Abdullah M Asiri³,HadiM M arwani³,赵轻舟⁴,盛国栋¹()

^1. 绍兴文理学院化学与化工学院, 绍兴 312000
^2. 杭州电子大学材料与环境工程学院, 杭州 310018
^3. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
^4. 中国科学院大学资源与环境学院, 北京 100049

收稿日期:2019-07-22 修回日期:2019-09-11 出版日期:2020-03-20 网络出版日期:2020-03-24
作者简介:李丽(1995–), 女, 硕士研究生. E-mail: 2740033871@qq.com

Distinguished Cd(II) Capture with Rapid and Superior Ability using Porous Hexagonal Boron Nitride: Kinetic and Thermodynamic Aspects

LI Li¹,GUO Xiaojie²,JIN Yang¹,CHEN Chaogui¹(),Abdullah M Asiri³,Hadi M Marwani³,ZHAO Qingzhou⁴,SHENG Guodong¹()

^1. College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing 312000, China
^2. College of Materials & Environmental Engineering, Hangzhou Dianzi University, Hangzhou 310018, China
^3. Chemistry Department, Faculty of Science, King Abdulaziz University, Jeddah 21589, Saudi Arabia
^4. College of Resources and Environment, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-07-22 Revised:2019-09-11 Published:2020-03-20 Online:2020-03-24
About author:LI Li(1995–), male, Master candidate. E-mail: 2740033871@qq.com
Supported by:
National Natural Science Foundation of China(21777102)

摘要/Abstract

摘要：

本工作对Cd(II)在多孔六方氮化硼(p-BN)上的吸附行为和机理进行了系统而全面的研究, 考察了溶液pH、吸附剂用量、接触时间和温度等条件对于Cd(II)吸附的影响, 并采用不同手段表征了吸附前后p-BN的化学组成、形态和表面官能团的变化, 进而研究其吸附机理。研究结果显示, 在pH 7.0和313 K条件下, Cd(II)的最大吸附容量可达到184 mg·g ^-1, 其动力学数据与拟二级模型和颗粒内扩散模型吻合, 表明吸附主要受化学吸附控制, 限速步骤主要是分子扩散。Cd(II)在p-BN上的吸附是一个自发和吸热过程, 吸附等温线分别符合Freundlich和Langmuir模型, 说明Cd(II)通过多层和单层吸附而吸附在非均相表面上。XPS的光谱结果显示, p-BN吸附剂具有大量的B-N, B-O等结构用作键合位点, 有利于从废水中吸收Cd(II)。这些结果表明, p-BN有希望作为吸附材料用于清除水体中的Cd(II)。

关键词: 氮化硼, 吸附, Cd(II), 重金属

Abstract:

In present work, a systematical and comprehensive understanding for the adsorption of Cd(II) on porous hexagonal boron nitride (p-BN) was studied. The chemical compositions, morphology and surface functional groups of p-BN before and after adsorption were characterized by SEM, HRTEM, BET, XRD, and FT-IR. The effects of pH, adsorbent dosage, contact time and temperature on Cd(II) adsorption were investigated. The maximum adsorption capacity for Cd(II) achieves 184 mg·g ^-1 at pH 7.0 and 313 K. The kinetic data fitted well with pseudo-second-order model and intra-particle diffusion model, indicating that the adsorption is mainly controlled by chemisorption, and the rate-limiting step is the molecular diffusion. The adsorption isotherms are in accordance with Freundlich and Langmuir model respectively, suggesting Cd(II) adsorbed on the heterogeneous surface through multilayer and monolayer adsorption. The thermodynamic parameters are calculated to confirm the spontaneous and endothermic process of Cd(II) sorption. Spectroscopic results from XPS imply that p-BN adsorbent had substantial functional groups and bonding sites, which is propitious to uptake Cd(II) from wastewater. These results revealed that p-BN is a promising candidate for Cd(II) scavenging.

Key words: boron nitride, adsorption, cadmium, heavy metal ion

中图分类号:

TQ174

李丽, 郭筱洁, 金阳, 陈朝贵, Abdullah M Asiri, HadiM M arwani, 赵轻舟, 盛国栋. 氮化硼纳米片吸附Cd(II)的动力学和热力学研究[J]. 无机材料学报, 2020, 35(3): 284-292.

LI Li, GUO Xiaojie, JIN Yang, CHEN Chaogui, Abdullah M Asiri, Hadi M Marwani, ZHAO Qingzhou, SHENG Guodong. Distinguished Cd(II) Capture with Rapid and Superior Ability using Porous Hexagonal Boron Nitride: Kinetic and Thermodynamic Aspects[J]. Journal of Inorganic Materials, 2020, 35(3): 284-292.

图/表 15

Fig. S1 Energy spectrum analysis (ESA) for unidentified black dots adsorbed on p-BN

Fig. 1 (A) SEM and (B) HRTEM images of p-BN, (C) SEM and (D) HRTEM images of p-BN after adsorption, (E) EDS analysis and (F) high-magnification HRTEM image of p-BN after adsorption

Fig. 2 XRD patterns (A) and FT-IR spectra (B) of p-BN before and after adsorption

Fig. S2 BET measurement of p-BN (a) N2 adsorption-desorption isotherm; (b) BJH pore-size distribution curve

Fig. 3 (A) Effect of initial pH on Cd(II) adsorption capacity (qe) and adsorption percentage at equilibrium, and (B) effect of p-BN dosage on the adsorption capacity (qe) and adsorption percentage of Cd(II)

Fig. S3 Variation of distribution of Cd(II) hydrolyzate species with pH

Fig. 4 (A) Adsorption capacities of Cd(II) with various contact times at different initial concentrations of Cd(II), and (B) adsorption percentages of Cd(II) on p-BN with various contact time at different initial concentrations of Cd(II)

Fig. S4 Kinetics models for adsorption of Cd(II) on p-BN (A) Pseudo-first-order model; (B) Pseudo-second-order model; (C) Intra-particle diffusion model; (D) Liquid-film diffusion model. Experimental conditions: Initial pH at 7.0, C0=60 mg·L-1, m=10.0 mg, V=50 mL

Table S1 Adsorption kinetics models parameters

Cd(II)/p-BN	Model
Cd(II)/p-BN	Pseudo-first-order		Pseudo-second-order		Intra-particle diffusion		Liquid-film diffusion
Parameters	q_e,cal=/(mg·g^-1)	111.7	q_e,cal=/(g·mg^-1·h^-1)	193.1	I	60.2	K_f/h^-1	0.524
	K₁^-1	0.524	K₂(g·mg^-1·h^-1)	1.00×10^-3	k_d/(g·mg^-1·h^-1/2)	49.4	A	-0.499
	R²	0.948	R²	0.999	R²	0.872	R²	0.948

Fig. 5 (A) Adsorption isotherms of Cd(II) on p-BN at T=303, 313 and 323 K, equilibrium adsorption isotherms fitted by (B) Langmuir model, (C) Freundlich model, (D) Tempkin model Experimental conditions: Initial pH at 7.0, C0=60 mg·L-1, m=10.0 mg, V=50 mL

Fig. S5 Linear plots of lnKd versus 1/T for Cd(II) adsorption on p-BN adsorbent

Table 1 Adsorption isotherm models parameters of Cd(II) on p-BN

Model parameter		Langmuir model			Freundlich model			Tempkin model
Model parameter		q_m/(mg·g^-1)	K_L/(L·mg^-1)	R²	1/n	K_F	R²	K_T/(L·mg^-1)	f	R²
T/K	303	236	0.112	0.984	0.229	1.27	0.987	43.1	2.19	0.987
	313	256	0.126	0.968	0.225	1.29	0.989	49.1	2.00	0.984
	323	290	0.121	0.983	0.223	1.32	0.994	58.3	1.63	0.991

Table S2 Values of thermodynamic parameters for the adsorption of Cd(II) on p-BN

Adsorbate	C₀/(mg·L^-1)	ΔH^θ/(kJ·mol^-1)	ΔS^θ/(J·mol^-1·K^-1)	ΔG^θ/(kJ·mol^-1)
Adsorbate	C₀/(mg·L^-1)	ΔH^θ/(kJ·mol^-1)	ΔS^θ/(J·mol^-1·K^-1)	303 K	313 K	323 K
Cd(II)	50	16.51	72.81	-5.55	-6.28	-7.01
	60	17.58	73.40	-4.66	-5.39	-6.13
	70	14.25	61.39	-4.35	-4.97	-5.58
	80	16.21	66.54	-3.95	-4.62	-5.28
	90	16.08	64.60	-3.49	-4.14	-4.79

Fig. 6 (A) XPS surveys for p-BN and adsorbed p-BN(inset: high resolution Cd3d XPS spectrum and background); (B) Experimental bonding enerygy peaks of Cd(II) and the comparisons of primary peaks of Cd3d5/2 and Cd3d3/2 for free Cd(II), CdCO3, Cd(OH)2

Fig. S6 High resolution spectra of B1s (a) and O1s (b) for p-BN before and after adsorption

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氮化硼纳米片吸附Cd(II)的动力学和热力学研究

Distinguished Cd(II) Capture with Rapid and Superior Ability using Porous Hexagonal Boron Nitride: Kinetic and Thermodynamic Aspects

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