立方体纳米Cu2O吸附热力学及动力学的粒度效应研究

doi:10.7503/cjcu20190117

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (10): 2214.doi: 10.7503/cjcu20190117

立方体纳米Cu₂O吸附热力学及动力学的粒度效应研究

肖碧源¹,邱江源¹,覃方红¹,万婷¹,徐亚群¹,农晓慧¹,黄在银^1,^2,^*()

^1. 广西民族大学化学化工学院, 南宁 530008
^2. 广西高校食品安全与药物分析化学重点实验室, 南宁 530008

收稿日期:2019-02-25 出版日期:2019-10-08 发布日期:2019-10-16
通讯作者: 黄在银 E-mail:huangzaiyin@163.com
基金资助:
国家自然科学基金(Nos.21273050);国家自然科学基金(Nos.21573048);国家自然科学基金(Nos.21873022);广西民族大学研究生科研创新项目(No.gxun-chxzs2016120)

Study on Particle Size Effect on Adsorption Thermodynamics and Kinetics of Cubic Nano-Cu₂O ^†

XIAO Biyuan¹,QIU Jiangyuan¹,QIN Fanghong¹,WAN Ting¹,XU Yaqun¹,NONG Xiaohui¹,HUANG Zaiyin^1,^2,^*()

^1. College of Chemistry and Chemical Engineering, Guangxi University for Nationalities, Nanning 530008, China
^2. Guangxi Colleges and Universities Key Laboratory of Food Safety and Pharmaceutical Analytical Chemistry, Nanning 530008, China

Received:2019-02-25 Online:2019-10-08 Published:2019-10-16
Contact: HUANG Zaiyin E-mail:huangzaiyin@163.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21273050);† Supported by the National Natural Science Foundation of China(Nos.21573048);† Supported by the National Natural Science Foundation of China(Nos.21873022);the Graduate Research Innovation Project of Guangxi University for Nationalities, China(No.gxun-chxzs2016120)

摘要/Abstract

摘要：

采用不同粒径的单一(100)晶面的立方体纳米Cu₂O作为模型材料, 研究了粒径和温度对其吸附动力学和吸附热力学性质的影响规律. 基于已建立的纳米材料吸附热力学和动力学理论, 推导出了单一(100)晶面立方体纳米Cu₂O材料的吸附热力学和吸附动力学性质与粒径之间的关系式. 实验结果与理论预测结果一致: 随着纳米Cu₂O粒径的减小, 吸附速率常数增大而吸附活化能和吸附指前因子减小; 标准摩尔吸附Gibbs自由能 Δ_a $G^{\rlap{-}0}_{m}$减小而标准吸附平衡常数ln $K^{\rlap{-}0}$、标准摩尔吸附焓 Δ_a $H^{\rlap{-}0}_{m}$和标准摩尔吸附熵 Δ_a$S^{\rlap{-}0}_{m}$均增大, 且以上参数均与粒度的倒数具有较好的线性关系.

关键词: 单一晶面, 立方体氧化亚铜, 吸附动力学, 吸附热力学, 粒度效应

Abstract:

The impacts of particle size and temperature on the adsorption kinetics and thermodynamics of nanomaterials were investigated by using single faceted cubic Cu₂O(100) with different particle sizes as model materials. Based on previously reported theory of adsorption thermodynamics and kinetics of nanomaterials, the relationships between the particle size of the cubic Cu₂O nanoparticles and their adsorption thermodynamics and kinetics were derived. The experimental results are in good agreement with the theoretical predictions. With the decrease of the size of the cubic Cu₂O(100) nanoparticles, the following characteristics were observed: (1) the adsorption rate constant increased, while the adsorption activation energy and the adsorption pre-exponential factors decreased; (2) the standard molar Gibbs free energy of adsorption(Δ_aG ^0— _m) decreased, while the standard equilibrium constant(lnK ^0—), the standard molar enthalpy of adsorption(Δ_aH ^0— _m), and the standard molar entropy of adsorption(Δ_aS ^0— _m) increased. The thermodynamic properties and kinetic parameters above have a good linear relationship with the reciprocal of particle size.

Key words: Single crystal face, Cubic Cu₂O, Adsorption kinetics, Adsorption thermodynamics, Particle size effect

中图分类号:

O642

TrendMD:

肖碧源,邱江源,覃方红,万婷,徐亚群,农晓慧,黄在银. 立方体纳米Cu₂O吸附热力学及动力学的粒度效应研究. 高等学校化学学报, 2019, 40(10): 2214.

XIAO Biyuan,QIU Jiangyuan,QIN Fanghong,WAN Ting,XU Yaqun,NONG Xiaohui,HUANG Zaiyin. Study on Particle Size Effect on Adsorption Thermodynamics and Kinetics of Cubic Nano-Cu₂O ^†. Chem. J. Chinese Universities, 2019, 40(10): 2214.

图/表 16

Fig.1 Standard curve of methyl orange

Fig.2 SEM images and the distribution histograms(inset) of nano-Cu2O with different sizes (A) Sample A; (B) sample B; (C) sample C; (D) sample D.

Fig.3 XRD patterns(A) and Raman spectra(B) of nano-Cu2O with different sizes a. Sample A; b. sample B; c. sample C; d. sample D.

Fig.4 Adsorption of methyl orange on nano-Cu2O with different sizes in aqueous solution at 298.15 K

Table 1 Kinetics parameters for adsorption of methyl orange on nano-Cu2O at 298.15 K

Sample	l/nm	q_e,_x/(mg·g^-1)	Pseudo-first order			Pseudo-second order
Sample	l/nm	q_e,_x/(mg·g^-1)	k₁	q_e,c/(mg·g^-1)	R²	k₂	q_e,c/(mg·g^-1)	R²
A	42	41.6844	0.03387	13.7536	0.8482	4.5226	43.1779	0.9994
B	54	35.6667	0.02976	12.6395	0.9197	4.1774	37.2578	0.9995
C	67	28.5160	0.04793	20.8775	0.9911	3.7272	30.6843	0.9986
D	117	23.3437	0.03404	15.0143	0.9923	3.2826	25.4001	0.9994

Fig.5 Fit lines of the pseudo-first-order kinetic equation(A) and the pseudo-second-order kinetic equation(B) of adsorption of methyl orange on nano-Cu2O with different sizes in aqueous solution at 298.15 K

Fig.6 Relationships between the logarithms of adsorption rate constants and the reciprocals of particle sizes of nano-Cu2O at different temperatures

Fig.7 Relationsships between the logarithms of adsorption rate constants of nano-Cu2O with different sizes and the reciprocals of temperatures

Table 2 Activation energy(Ea) and natural logarithm of pre-exponential factor(lnA) of adsorption of methyl orange on nano-Cu2O

Sample	l/nm	E_a/(kJ·mol^-1)	lnA/(g·mg^-1·min^-1)	Sample	l/nm	E_a/(kJ·mol^-1)	lnA/(g·mg^-1·min^-1)
A	42	16.8861	8.3560	C	67	18.0203	8.5920
B	54	17.6544	8.5462	D	117	18.9848	8.8479

Fig.8 Relationships between the activation energy and the reciprocal of particle size(A) and between the logarithm of pre-exponential factor and the reciprocal of particle size(B) of nano-Cu2O adsorption system

Table 3 Logarithms of the standard equilibrium constants of the cubic nano-Cu2O with different diameters at different temperatures

T/K	lnK^0—				T/K	lnK^0—
T/K	Sample A	Sample B	Sample C	Sample D	T/K	Sample A	Sample B	Sample C	Sample D
288.15	1.2996	0.9165	0.5659	0.4403	318.15	2.9303	2.2448	1.9259	1.7246
298.15	1.8977	1.5503	1.2579	0.8801	328.15	3.4863	2.7338	2.2453	1.9293
308.15	2.4215	1.8715	1.5852	1.4039

Fig.9 Relationships between the logarithm of the standard and the reciprocal of the diameter of nano-Cu2O equilibrium constants at different temperatures

Table 4 Change in standard Gibbs free energy of the adsorption of the nano-Cu2O with various sizes at different temperatures

T/K	Δ_aG^0— _m/(kJ·mol^-1)				T/K	Δ_aG^0— _m/(kJ·mol^-1)
T/K	Sample A	Sample B	Sample C	Sample D	T/K	Sample A	Sample B	Sample C	Sample D
288.15	-3.1134	-2.1956	-1.3556	-1.0547	318.15	-7.7509	-5.9378	-5.0943	-4.5616
298.15	-4.7041	-3.8428	-3.1180	-2.1816	328.15	-9.5114	-7.4585	-6.1256	-5.2635
308.15	-6.2038	-4.7947	-4.0612	-3.5967

Fig.10 Relationships between the standard molar adsorption Gibbs free energy and temperature of nano-Cu2O(A), and between the standard molar adsorption Gibbs free energy and reciprocal grain size of nano-Cu2O(B)

Table 5 Standard molar adsorption enthalpies and standard molar adsorption entropies of cubic nano-Cu2O with different diameters

Sample	l/nm	Δ_aH^0— _m/(kJ·mol^-1)	Δ_aS^0— _m/(J·mol^-1·K^-1)	Sample	l/nm	Δ_aH^0— _m/(kJ·mol^-1)	Δ_aS^0— _m/(J·mol^-1·K^-1)
A	42	42.56	158.43	C	67	31.54	115.16
B	54	34.04	126.21	D	117	29.94	107.98

Fig.11 Relationships between the standard molar adsorption entropies and the reciprocals of particle size(A) and between the standard molar adsorption enthalpies and the reciprocals of particle size(B) of nano-Cu2O adsorption system

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立方体纳米Cu₂O吸附热力学及动力学的粒度效应研究

Study on Particle Size Effect on Adsorption Thermodynamics and Kinetics of Cubic Nano-Cu₂O ^†

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