Microscopic Insights into pH-dependent Adsorption of Cd(II) on Molybdenum Disulfide Nanosheets

doi:10.15541/jim20190381

Abstract

Abstract:

Herein, the retention mechanisms and microstructure of Cd(II) on MoS₂nanosheets were evaluated by batch experiments and EXAFS technology. The sorption of Cd(II) on MoS₂was strongly affected by solution pH, contact time, and temperature, but not by the ionic strength. The solution pH could only promote the sorption capacity, but does not improve the sorption rates and change the sorption isotherms and thermodynamics in the pH range of 3.3-9.6. The pseudo-second-order model could fit the equilibrium data better and the intra-particle diffusion model showed three typical stages in the sorption process. The isotherms and thermodynamics analysis indicated that the heterogeneity sorption of Cd(II) onto MoS₂was a spontaneous, endothermic, and irreversible process. The EXAFS spectra revealed the coexistence of two sorption types. The inner-sphere complexation was formed in the form of Cd-S bond at lower pH (3.56, 6.48), while the Cd(OH)₂precipitation occurred in the form of Cd-O and Cd-Cd bonds at higher pH (9.57). These results provide new insights into the interaction mechanisms between metal ions and MoS₂ nanosheets.

Key words: MoS₂ nanosheets, pH, microstructure, EXAFS, cadmium(II)

CLC Number:

TQ174

DONG Lijia, GUO Xiaojie, LI Xue, CHEN Chaogui, JIN Yang, AHMED Alsaedi, TASAWAR Hayat, ZHAO Qingzhou, SHENG Guodong. Microscopic Insights into pH-dependent Adsorption of Cd(II) on Molybdenum Disulfide Nanosheets[J]. Journal of Inorganic Materials, 2020, 35(3): 293-300.

Figures/Tables 13

References 53

[1]	ZENG G, LIU Y, TANG L , et al. Enhancement of Cd(II) adsorption by polyacrylic acid modified magnetic mesoporous carbon. Chem. Eng. J., 2015,259:153-160.
[2]	YANG G, TANG L, LEI X , et al. Cd(II) removal from aqueous solution by adsorption on ketoglutaric acid-modified magnetic chitosan. Appl. Surf. Sci., 2014,292:710-716.
[3]	LUO L, MA Y B, ZHANG S Z , et al. An inventory of trace element inputs to agricultural soils in China. J. Environ. Manage, 2009,90(8):2524-2530.
[4]	KHAN T A, CHAUDHRY S A, ALI I . Equilibrium uptake, isotherm and kinetic studies of Cd(II) adsorption onto iron oxide activated red mud from aqueous solution. J. Mol. Liq., 2015,202:165-175.
[5]	AWUAL M R, KHRAISHEH M, ALHARTHI N H , et al. Efficient detection and adsorption of cadmium(II) ions using innovative nano-composite materials. Chem. Eng. J., 2018,343:118-127.
[6]	LIAO Q, ZOU D, PAN W , et al. Highly-efficient scavenging of P(V), Cr(VI), Re(VII) anions onto g-C₃N₄ nanosheets from aqueous solutions as impacted via water chemistry. J. Mol. Liq., 2018,258:275-284.
[7]	DONG L, YANG J, MOU Y , et al. Effect of various environmental factors on the adsorption of U(VI) onto biochar derived from rice straw. J. Radioanal. Nucl. Chem., 2017,314(1):377-386.
[8]	SHENG G D, YANG Q, PENG F , et al. Determination of colloidal pyrolusite, Eu(III) and humic substance interaction: a combined batch and EXAFS approach. Chem. Eng. J., 2014,245:10-16.
[9]	YU S J, WANG X X, PANG H W , et al. Boron nitride-based materials for the removal of pollutants from aqueous solutions: a review. Chem. Eng. J., 2018,333:343-360.
[10]	YAO W, WANG X, LIANG Y , et al. Synthesis of novel flower-like layered double oxides/carbon dots nanocomposites for U(VI) and ²⁴¹Am(III) efficient removal: batch and EXAFS studies. Chem. Eng. J., 2018,332:775-786.
[11]	WANG J, WANG X X, ZHAO G X , et al. Polyvinylpyrrolidone and polyacrylamide intercalated molybdenum disulfide as adsorbents for enhanced removal of chromium(VI) from aqueous solutions. Chem. Eng. J., 2018,334:569-578.
[12]	LIAO Q, ZOU D S, PAN W , et al. Highly efficient capture of Eu(III), La(III), Nd(III), Th(IV) from aqueous solutions using g-C₃N₄ nanosheets. J. Mol. Liq., 2018,252:351-361.
[13]	WANG X X, YU S J, WANG X K . Removal of radionuclides by metal-organic framework-based materials. J. Inorg. Mater., 2019,34(1):17-26.
[14]	WANG N, PANG H, YU S , et al. Investigation of adsorption mechanism of layered double hydroxides and their composites on radioactive uranium: a review. Acta Chim. Sinica, 2019,77(2):143-152.
[15]	LIU X, MA R, WANG X , et al. Graphene oxide-based materials for efficient removal of heavy metal ions from aqueous solution: a review. Environ. Pollut., 2019,252:62-73.
[16]	WANG X X, CHEN L, WANG L , et al. Synthesis of novel nanomaterials and their application in efficient removal of radionuclides. Sci. China Chem., 2019,62(8):933-967.
[17]	FENG B, YAO C, CHEN S , et al. Highly efficient and selective recovery of Au(III) from a complex system by molybdenum disulfide nanoflakes. Chem. Eng. J., 2018,350:692-702.
[18]	CHEN H J, HUANG J, LEI X L , et al. Adsorption and diffusion of lithium on MoS₂ monolayer: the role of strain and concentration. Int. J. Electrochem. Sci., 2013,8:2196-2203.
[19]	JIA F, WANG Q, WU J , et al. Two-dimensional molybdenum disulfide as a superb adsorbent for removing Hg⁺ from water. ACS Sustainable Chem. Eng., 2017,5:7410-7419.
[20]	JIA F, ZHANG X, SONG S . AFM study on the adsorption of Hg ²+ on natural molybdenum disulfide in aqueous solutions . Phys. Chem. Chem. Phys., 2017,19:3837-3844.
[21]	WANG Z, MI B . Environmental applications of 2D molybdenum disulfide (MoS₂) nanosheet. Environ. Sci. Technol., 2017,51:8229-8244.
[22]	AI K, RUAN C, SHEN M , et al. MoS₂ nanosheets with widened interlayer spacing for high-efficiency removal of mercury in aquatic systems. Adv. Funct. Mater., 2016,26:5542-5549.
[23]	TONG S, DENG H, WANG L , et al. Multi-functional nanohybrid of ultrathin molybdenum disulfide nanosheets decorated with cerium oxide nanoparticles for preferential uptake of lead (II) ions. Chem. Eng. J., 2018,335:22-31.
[24]	LI X, LI Q, LINGHU W , et al. Sorption properties of U(VI) and Th(IV) on two-dimensional molybdenum disulfide (MoS₂) nanosheets: effects of pH, ionic strength, contact time, humic acids and temperature. Environ. Technol. Innov., 2018,11:328-338.
[25]	WANG Q, YANG L, JIA F , et al. Removal of Cd(II) from water by using nano-scale molybdenum disulphide sheets as adsorbents. J. Mol. Liq., 2018,263:526-533.
[26]	ZHI L, ZUO W, CHEN F , et al. 3D MoS₂ composition aerogel as chemosensors and adsorbents for colorimetric detection and high- capacity adsorption of Hg²⁺. ACS Sustain. Chem. Eng., 2016,4:3398-3408.
[27]	AI K, RUAN C, SHEN M , et al. MoS₂ nanosheets with widened interlayer spacing for high-efficiency removal of mercury in aquatic systems. Adv. Funct. Mater., 2016,26:5542-5549.
[28]	AGHAGOLI M J, BEYKI M H, SHEMIRANI F . Application of dahlia-like molybdenum disulfide nanosheets for solid phase extraction of Co(II) in vegetable and water samples. Food Chem., 2017,223:8-15.
[29]	GAO X, SHENG G D, HUANG Y Y . Mechanism and microstructure of Eu(III) interaction with γ-MnOOH by a combination of batch and high resolution EXAFS investigation. Sci. China Chem., 2013,56:1658-1666.
[30]	DONG L, LIAO Q, LINGHU W , et al. Application of EXAFS with a bent crystal analyzer to study the pH-dependent microstructure of Eu(III) onto birnessite. J. Environ. Chem. Eng., 2018,6:842-848.
[31]	VASCONCELOS I F, HAACK E A, MAURICE P A , et al. EXAFS analysis of cadmium(II) adsorption to kaolinite. Chem. Geol., 2008,249:237-249.
[32]	LIU C, FRENKEL A I, VAIRAVAMURTHY A , et al. Sorption of cadmium on humic acid: mechanistic and kinetic studies with atomic force microscopy and X-ray absorption fine structure spectroscopy. Can. J. Soil Sci., 2001,81:337-348.
[33]	SHENG G D, YANG S T, LI Y M , et al. Retention mechanisms and microstructure of Eu(III) on manganese dioxides studied by batch and high resolution EXAFS technique. Radiochim. Acta, 2014,102:155-167.
[34]	COLEMAN J N, LOTYA M, O’NEILL A , et al. Two dimensional nanosheets produced by liquid exfoliation of layered materials. Science, 2011,331(6017):568-571.
[35]	SPLENDIANI A, SUN L, ZHANG Y , et al. Emerging photoluminescence in monolayer MoS₂. Nano Lett., 2010,10:1271-1275.
[36]	KUMAR A S K, JIANG S J, WARCHOL J K . Synthesis and characterization of two-dimensional transition metal dichalcogenide magnetic MoS₂@Fe₃O₄ nanoparticles for adsorption of Cr(VI)/Cr(III). ACS Omega, 2017,2:6187-6200.
[37]	TAKAMATSU R, ASAKURA K, CHUN W J , et al. EXAFS studies about the sorption of cadmium ions on montmorillonite. Chem. Lett., 2006,35:224-225.
[38]	HUANG X, CHEN T, ZOU X , et al. The adsorption of Cd(II) on manganese oxide investigated by batch and modeling techniques. Int. J. Environ. Res. Public Health, 2017,14(10):1145.
[39]	GUECHI E, BEGGAS D . Removal of cadmium (II) from water using fibre fruit lufa as biosorbent. Desalin. Water Treat., 2017,94:181-188.
[40]	ABASIYAN S M A, MAHDANINIA G R . Polyvinyl alcohol- based nanocomposite hydrogels containing magnetic laponite RD to remove cadmium. Environ. Sci. Poll. Res., 2018,25:14977-14988.
[41]	CORBETT J F . Pseudo first-order kinetics. J. Chem. Educ., 1972,49:663.
[42]	HO Y S, MCKAY G . A comparison of chemisorption kinetic models applied to pollutant removal on various sorbents. Process. Saf. Environ., 1998,76:332-340.
[43]	GRAAF G H, SCHOLTENS H, STAMHUIS E J , et al. Intra-particle diffusion limitations in low-pressure methanol synthesis. Chem. Eng. Sci., 1990,45:773-783.
[44]	HO Y S, MCKAY G . The kinetics of sorption of divalent metal ions onto sphagnum moss peat. Water Rer., 2000,34:735-742.
[45]	TEMKIN M J, PYZHEV V . Recent modifications to Langmuir isotherms. Acta Physchim, 1940,12:217-222.
[46]	XUE C, QI P S, LIU Y Z . Adsorption of aquatic Cd ²+ using a combination of bacteria and modified carbon fiber . Adsorpt. Sci. Technol., 2017,36:857-871.
[47]	GU P, ZHANG S, ZHANG C , et al. Two-dimensional MAX- derived titanate nanostructures for efficient removal of Pb(II). Dalton Trans., 2019,48(6):2100-2107.
[48]	CHEN W, LU Z, XIAO B , et al. Enhanced removal of lead ions from aqueous solution by iron oxide nanomaterials with cobalt and nickel doping. J. Clean. Prod., 2019,211:1250-1258.
[49]	ZHANG D, NIU H Y, ZHANG X L , et al. Strong adsorption of chlorotetracycline on magnetite nanoparticles. J. Hazard. Mater., 2011,192:1088-1093.
[50]	ZHANG H, YU X, CHEN L , et al. Study of ⁶³Ni adsorption on NKF-6 zeolite. J. Environ. Radioact., 2010,101:1061-1069.
[51]	BEKCI Z, SEKI Y, YURDAKOC M K . A study of equilibrium and FTIR, SEM/EDS analysis of trimethoprim adsorption onto K10. J. Mol. Struct., 2007,827:67-74.
[52]	GRÄFE M, SINGH B, BALASUBRAMANIAN M . Surface speciation of Cd(II) and Pb(II) on kaolinite by EXAFS spectroscopy. J. Colloid Interf. Sci., 2007,315:21-32.
[53]	SHENG G, DONG H, SHEN R , et al. Microscopic insights into the temperature dependent adsorption of Eu(III) onto titanate nanotubes studied by FTIR, XPS, XAFS and batch technique. Chem. Eng. J., 2013,217:486-494.

	pH	T/K	K_F/(mg^1-ⁿ·Lⁿ∙g^-1)	n	R²
Freundlich equation	4.55	293	1.624	1.440	0.887
		313	4.256	1.160	0.881
		333	7.461	1.052	0.904
	5.34	293	9.363	0.899	0.801
		313	21.627	0.603	0.907
		333	32.734	0.526	0.939
	6.12	293	17.298	0.650	0.812
		313	28.054	0.542	0.935
		333	34.119	0.499	0.919
	pH	T/K	q_max/(mg∙g^-1)	K_L/(L∙mg^-1)	R²
Langmuir equation	4.55	293	0.040	64.516	0.299
		313	0.016	305.157	0.069
		333	0.001	754.717	0.017
	5.34	293	0.036	262.536	0.162
		313	0.132	149.276	0.918
		333	0.236	147.580	0.978
	6.12	293	0.114	140.449	0.759
		313	0.172	152.022	0.974
		333	0.224	151.492	0.978

	pH	T/K	K_F/(mg^1-ⁿ·Lⁿ∙g^-1)	n	R²
Freundlich equation	4.55	293	1.624	1.440	0.887
		313	4.256	1.160	0.881
		333	7.461	1.052	0.904
	5.34	293	9.363	0.899	0.801
		313	21.627	0.603	0.907
		333	32.734	0.526	0.939
	6.12	293	17.298	0.650	0.812
		313	28.054	0.542	0.935
		333	34.119	0.499	0.919
	pH	T/K	q_max/(mg∙g^-1)	K_L/(L∙mg^-1)	R²
Langmuir equation	4.55	293	0.040	64.516	0.299
		313	0.016	305.157	0.069
		333	0.001	754.717	0.017
	5.34	293	0.036	262.536	0.162
		313	0.132	149.276	0.918
		333	0.236	147.580	0.978
	6.12	293	0.114	140.449	0.759
		313	0.172	152.022	0.974
		333	0.224	151.492	0.978

	pH	q_e/(mg·g^-1)	k₁/h^-1	R²
	4.55	33.023	0.059	0.9896
Pseudo-first- order model	5.34	23.903	0.053	0.9069
	6.12	41.777	0.074	0.9835
	pH	q_e/(mg·g^-1)	k₂/(g·mg^-1·h^-1)	R²
	4.55	35.638	0.038	0.9869
Pseudo-second- order model	5.34	42.230	0.078	0.9978
	6.12	52.659	0.077	0.9986
	pH	C/(mg·L^-1)	k_i/(g·mg^-1·h^-1/2)	R²
	4.55	19.985	2.628	0.942
Intra-particle diffusion model	5.34	32.500	1.877	0.987
	6.12	39.759	3.004	0.980

	pH	q_e/(mg·g^-1)	k₁/h^-1	R²
	4.55	33.023	0.059	0.9896
Pseudo-first- order model	5.34	23.903	0.053	0.9069
	6.12	41.777	0.074	0.9835
	pH	q_e/(mg·g^-1)	k₂/(g·mg^-1·h^-1)	R²
	4.55	35.638	0.038	0.9869
Pseudo-second- order model	5.34	42.230	0.078	0.9978
	6.12	52.659	0.077	0.9986
	pH	C/(mg·L^-1)	k_i/(g·mg^-1·h^-1/2)	R²
	4.55	19.985	2.628	0.942
Intra-particle diffusion model	5.34	32.500	1.877	0.987
	6.12	39.759	3.004	0.980

pH	T	ΔG^θ/(kJ/mg)	ΔS^θ/(J∙mg^-1· K^-1)	ΔH^θ/(kJ∙mg^-1)
4.55	293	-19.291	143.66592	22.803
	313	-22.333		22.635
	333	-25.022		22.818
5.34	293	-22.331	147.73978	20.957
	313	-25.312		20.930
	333	-28.239		20.958
6.12	293	-23.412	121.71696	12.251
	313	-25.986		12.111
	333	-28.267		12.265