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

doi:10.7503/cjcu20190117

Abstract

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

CLC Number:

O642

TrendMD:

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 ^†[J]. Chem. J. Chinese Universities, 2019, 40(10): 2214.

Figures/Tables 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

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

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

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

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)

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

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