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

doi:10.15541/jim20190371

Abstract

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

CLC Number:

TQ174

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.

Figures/Tables 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. 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">

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

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">

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

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

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">

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

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