PEI Modified Hydrated Calcium Silicate Derived from Fly Ash and Its adsorption for Removal of Cu (II) and Catalytic Degradation of Organic Pollutants

doi:10.15541/jim20230209

Abstract

Abstract:

With the rapid development of industry, copper metal pollution in wastewater discharged from related manufacturing fields has become increasingly serious.Meanwhile, demand for copper metal resources in the field of catalysis is increasing. In this study, low-cost modified calcium silicate hydrate (PCSH) was prepared using fly ash and modifier polyethyleneimine (PEI) for the adsorption of heavy metal copper ions(Cu(II)) in aqueous solution, and then the Cu(II), immobilized on the surface, was further treated with alkali to form copper-based active material for catalytic degradation of organic pollutants. Compared with unmodified sample (CSH), the maximum adsorption capacity of PCSH for Cu(II) was increased by 100% with the maximum of 588 mg/g. The main reason was that the addition of PEI facilitated formation of larger specific surface area, excellent pore structure and strong complexation between Cu(II) and -NH₂. The copper-based catalysts, which obtained from PCSH exhibiting spindle-shaped porous morphology, could catalyze the oxidative degradation of rhodamine B (RhB) by activating potassium peroxymonosulfate (PMS) and the reduction of 4-nitrophenol (4-NP) by activating sodium borohydride (NaBH₄), with rate constants of 0.7135/min (pH (7.0±0.3); [RhB]= 20 mg/L; [PMS]= 0.12 g/L; [catalyst]= 0.8 g/L) and 11.47×10^-3/s (pH (11.0±0.3); [4-NP]= 10^-4 mol/L; [NaBH₄]= 5×10^-3 mol/L; [catalyst]= 0.167 g/L), respectively, about 20 and 19 times as large as those of CSH catalyst system, respectively. The present work achieves the reuse of copper element in aqueous solution by using solid waste fly ash, which provides new insights into effective treatment and utilization of pollutants in water.

Key words: fly ash, calcium silicate hydrate, Cu(II) adsorption, polyethyleneimine, potassium peroxymonosulfate

CLC Number:

X522

TANG Ya, SUN Shengrui, FAN Jia, YANG Qingfeng, DONG Manjiang, KOU Jiahui, LIU Yangqiao. PEI Modified Hydrated Calcium Silicate Derived from Fly Ash and Its adsorption for Removal of Cu (II) and Catalytic Degradation of Organic Pollutants[J]. Journal of Inorganic Materials, 2023, 38(11): 1281-1291.

Figures/Tables 18

Fig. 1 (a) XRD patterns, (b) FT-IR spectra and (c) N2 adsorption-desorption isotherms of CSH and PCSH

Fig. 2 Different magnification SEM images of (a, b) CSH and (c, d) PCSH

Fig. 3 Adsorption characteristics of samples (a) Variation of adsorption capacity of samples with time; (b) Effect of pH on the adsorption capacity of PCSH; (c) Adsorption isotherms of samples; (d) Variation of adsorption capacity of samples with initial concentration of Zn(II)-Pb(II)

Fig. 4 Characteristics of Cu-absorbed samples (a) XRD patterns; (b) Survey scans and high-resolution scans of (c) Cu2p, (d) N1s XPS spectra

Fig. 5 SEM images of (a) CSH-Cu, (b) PCSH-Cu, (c) CSH- Cu-c, and (d) PCSH-Cu-c

Fig. 6 (a) XRD patterns and (b) FT-IR spectra of CSH-Cu-c and PCSH-Cu-c

Fig. 7 Degradation of RhB by PMS with CSH-Cu-c and PCSH-Cu-c (a) RhB residue percentage; (b) Photo of catalytic device; (c) Catalytic performance of PCSH-Cu-c-M

Table 1 Rate constants (k) for the degradation of RhB by PMS with different catalysts

Catalyst	C₁/(g·L^-1)	C_PMS/(g·L^-1)	C_RhB/(mg·L^-1)	k/min^-1	Ref.
MPC	1	0.616	20	0.013	[27]
α-MnO₂/Pal	0.1	0.1	20	0.0204	[28]
Vis/BiVO₄	0.5	0.616	10	0.04	[29]
rGO-CoPc	0.3	0.616	10	0.288	[30]
CSH-Cu-c	0.8	0.12	20	0.036	This work
PCSH-Cu-c	0.8	0.12	20	0.7135	This work

Fig. 8 Suface elements and chemical status of samples (a) Cu2p and (b) O1s XPS spectra of PCSH-Cu-c before and after reaction; (c) Cu2p and (d) O1s XPS spectra of CSH-Cu-c and PCSH-Cu-c before reaction

Fig. 9 Free radical capture experiments of PCSH-Cu-c

Fig. 10 Change of 4-NP residue percentage Inset: photograph of the 4-NP solution after 3 min degradation

Table 2 Rate constants (k) for the degradation of 4-NP by NaBH4 with different catalysts

Catalyst	C₁/ (g·L^-1)	C_NaBH4/(mmol·L^-1)	C_4-NP/ (mmol·L^-1)	k/(×10^-3, s^-1)	Ref.
CuO NLs	0.307	10	0.12	0.36	[38]
Ag-NP/C	0.333	6.667	4.7×10^-2	1.69	[39]
Cu₂₋_xSe/ rGO/PVP	2.5	62.5	0.125	2.3	[40]
Pd-FG	0.5	10	0.1	2.35	[41]
CSH-Cu-c	0.167	5	0.1	0.61	This work
PCSH-Cu-c	0.167	5	0.1	11.47	This work

Fig. S1 EDS analyses of CSH

Fig. S2 EDS analysis of PCSH

Fig. S3 Linear fitting curves of (a) Langmuir model and (b) Freundlich model for isotherms of CSH and PCSH

Fig. S4 EDS analyses of PCSH-Cu

Table S1 Langmuir and Freundlich isotherm fitting parameters

Sample	Langmuir model			Freundlich model
Sample	q_m	K_L	R²	n	K_F	R²
CSH	294.10	0.0200	0.9945	3.810	54.00	0.8670
PCSH	588.23	0.0563	0.9982	5.848	198.86	0.9450

Table S2 Comparison of maximum adsorption capacities of various sorbents as reported in the literature for Cu(II)

Sample	q / (mg·g^-1)	S_BET/ (m²·g^-1)	Ref.
Activated carbon	10	921	[S1]
Modified SBA-15 mesoporous silica	46	317	[S2]
MCM-48	126	511	[S3]
Citrate-LDH	137	8	[S4]
Mesoporous silica	153	462	[S5]
Humulus scandens-derived biochars	221	450	[S6]
Steel slag-derived CSH	244	77	[S7]
Amorphous molybdenum sulphide	259	28	[S8]
NPCS-PEI	276	491	[S9]
CSH	294	240	This work
PCSH	588	371	This work

References 41

[1]	CHEN H, WANG X, LI J, et al. Cotton derived carbonaceous aerogels for the efficient removal of organic pollutants and heavy metal ions. Journal of Materials Chemistry A, 2015, 3(11): 6073. DOI URL
[2]	GAWANDE M B, GOSWAMI A, FELPIN F X, et al. Cu and Cu-based nanoparticles: synthesis and applications in review catalysis. Chemical Reviews, 2016, 116(6): 3722. DOI URL
[3]	KOHANTORABI M, MOUSSAVI G, GIANNAKIS S. A review of the innovations in metal- and carbon-based catalysts explored for heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic contaminants. Chemical Engineering Journal, 2021, 411: 127957. DOI URL
[4]	ADITYA T, JANA J, SINGH N K, et al. Remarkable facet selective reduction of 4-nitrophenol by morphologically tailored (111) faceted Cu₂O nanocatalyst. ACS Omega, 2017, 2(5): 1968. DOI URL
[5]	TONG T, ZHAO S, BOO C, et al. Relating silica scaling in reverse osmosis to membrane surface properties. Environmental Science & Technology, 2017, 51(8): 4396. DOI URL
[6]	BERA A, TRIVEDI J S, KUMAR S B, et al. Anti-organic fouling and anti-biofouling poly(piperazineamide) thin film nanocomposite membranes for low pressure removal of heavy metal ions. Journal of Hazardous Materials, 2018, 343: 86. DOI PMID
[7]	FU F, WANG Q. Removal of heavy metal ions from wastewaters: a review. Journal of Environmental Management, 2011, 92(3): 407. DOI PMID
[8]	SUN L, WU J, WANG J, et al. CO₂-assisted ‘Weathering’ of steel slag-derived calcium silicate hydrate: A generalized strategy for recycling noble metals and constructing SiO₂-based nanocomposites. Journal of Colloid and Interface Science, 2022, 622: 1008. DOI URL
[9]	SHAO N, TANG S, LIU Z, et al. Hierarchically structured calcium silicate hydrate-based nanocomposites derived from steel slag for highly efficient heavy metal removal from wastewater. ACS Sustainable Chemistry & Engineering, 2018, 6(11): 14926.
[10]	CHEN L, WANG X, CHEN Y, et al. Recycling heavy metals from wastewater for photocatalytic CO₂ reduction. Chemical Engineering Journal, 2020, 402: 125922. DOI URL
[11]	CHEN Z, LI Y, CAI Y, et al. Application of covalent organic frameworks and metal-organic frameworks nanomaterials in organic/inorganic pollutants removal from solutions through sorption-catalysis strategies. Carbon Research, 2023, 2(1): 8. DOI
[12]	TAUSTER S J, FUNG S C. Strong metal-support interactions- occurrence among binary oxides of groups IIA-VB. Journal of Catalysis, 1978, 55(1): 29. DOI URL
[13]	GU H, LIU X, WANG S, et al. COF-based composites: extraordinary removal performance for heavy metals and radionuclides from aqueous solutions. Reviews of Environmental Contamination and Toxicology, 2022, 260(1): 23. DOI
[14]	WANG X, LI X, WANG J, et al. Recent advances in carbon nitride-based nanomaterials for the removal of heavy metal ions from aqueous solution. Journal of Inorganic Materials, 2020, 35(3): 260. DOI
[15]	GUO H, SUN P, LIANG Y, et al. In-situ fabrication of polyelectrolyte-CSH superhydrophilic coatings via layer-by-layer assembly. Chemical Engineering Journal, 2014, 253: 198. DOI URL
[16]	MEISZTERICS A, ROSTA L, PETERLIK H, et al. Structural characterization of gel-derived calcium silicate systems. Journal of Physical Chemistry A, 2010, 114(38): 10403. DOI PMID
[17]	KLONKOWSKI A M, GROBENLA B, WIDERNIK T, et al. The coordination state of copper(II) complexes anchored and grafted onto the surface of organically modified silicates. Langmuir, 1999, 15(18): 5814. DOI URL
[18]	GODIYA C B, REVADEKAR C, KIM J, et al. Amine- bilayer-functionalized cellulose-chitosan composite hydrogel for the efficient uptake of hazardous metal cations and catalysis in polluted water. Journal of Hazardous Materials, 2022, 436: 129112. DOI URL
[19]	VICENNATI P, GIULIANO A, ORTAGGI G, et al. Polyethylenimine in medicinal chemistry. Current Medicinal Chemistry, 2008, 15(27): 2826. PMID
[20]	NOSRATI A, LARSSON M, LINDEN J B, et al. Polyethyleneimine functionalized mesoporous diatomite particles for selective copper recovery from aqueous media. International Journal of Mineral Processing, 2017, 166: 29. DOI URL
[21]	HUANG Y, WU H, SHAO T, et al. Enhanced copper adsorption by DTPA-chitosan/alginate composite beads: Mechanism and application in simulated electroplating wastewater. Chemical Engineering Journal, 2018, 339: 322. DOI URL
[22]	CHADWICK D, KAROLEWSKI M A. Calibration of XPS core-level binding-energies-influence of the surface chemical-shift. Journal of Electron Spectroscopy and Related Phenomena, 1981, 24(2): 181. DOI URL
[23]	SUTIRMAN Z A, SANAGI M M, ABD KARIM K J, et al. Equilibrium, kinetic and mechanism studies of Cu(II) and Cd(II) ions adsorption by modified chitosan beads. International Journal of Biological Macromolecules, 2018, 116: 255. DOI PMID
[24]	PENG B, SONG T, WANG T, et al. Facile synthesis of Fe₃O₄@Cu(OH)₂ composites and their arsenic adsorption application. Chemical Engineering Journal, 2016, 299: 15. DOI URL
[25]	ZHAO C M, WANG G C, LI S L, et al. Reaction pathway led by silicate structure transformation on decomposition of CaSiO₃ in alkali fusion process using NaOH. Transactions of Nonferrous Metals Society of China, 2015, 25(11): 3827. DOI URL
[26]	ZHANG S, ZHANG X, BAI C, et al. Effect of TiO₂ content on the structure of CaO-SiO₂-TiO₂ system by molecular dynamics simulation. ISIJ International, 2013, 53(7): 1131. DOI URL
[27]	ZHU K, LIU C, XIA W, et al. Non-radical pathway dominated degradation of organic pollutants by nitrogen-doped microtube porous graphitic carbon derived from biomass for activating peroxymonosulfate: performance, mechanism and environmental application. Journal of Colloid and Interface Science, 2022, 625: 890. DOI PMID
[28]	HUANG C, WANG Y, GONG M, et al. α-MnO₂/palygorskite composite as an effective catalyst for heterogeneous activation of peroxymonosulfate PMS for the degradation of Rhodamine B. Separation and Purification Technology, 2020, 230: 115877. DOI URL
[29]	LIU Y, GUO H, ZHANG Y, et al. Activation of peroxymonosulfate by BiVO₄ under visible light for degradation of Rhodamine B. Chemical Physics Letters, 2016, 653: 101. DOI URL
[30]	MARINESCU C, BEN ALI M, HAMDI A, et al. Cobalt phthalocyanine-supported reduced graphene oxide: a highly efficient catalyst for heterogeneous activation of peroxymonosulfate for Rhodamine B and pentachlorophenol degradation. Chemical Engineering Journal, 2018, 336: 465. DOI URL
[31]	ZHAO Y, AN H, FENG J, et al. Impact of crystal types of AgFeO₂ nanoparticles on the peroxymonosulfate activation in the water. Environmental Science & Technology, 2019, 53(8): 4500. DOI URL
[32]	QIN Q, QIAO N, LIU Y, et al. Spongelike porous CuO as an efficient peroxymonosulfate activator for degradation of Acid Orange 7. Applied Surface Science, 2020, 521: 146479. DOI URL
[33]	LAN Q, SUN S R, WU P, et al. Co-doped CuO/visible light synergistic activation of PMS for degradation of Rhodamine B and its mechanism. Journal of Inorganic Materials, 2021, 36(11): 1171. DOI
[34]	XIAO R, LUO Z, WEI Z, et al. Activation of peroxymonosulfate/ persulfate by nanomaterials for sulfate radical-based advanced oxidation technologies. Current Opinion in Chemical Engineering, 2018, 19: 51. DOI URL
[35]	DUAN X, SU C, MIAO J, et al. Insights into perovskite-catalyzed peroxymonosulfate activation: maneuverable cobalt sites for promoted evolution of sulfate radicals. Applied Catalysis B-Environmental, 2018, 220: 626. DOI URL
[36]	ZHAO Y, WANG H, LI X, et al. Recovery of CuO/C catalyst from spent anode material in battery to activate peroxymonosulfate for refractory organic contaminants degradation. Journal of Hazardous Materials, 2021, 420: 126552. DOI URL
[37]	SINGH C, GOYAL A, SINGHAL S. Nickel-doped cobalt ferrite nanoparticles: efficient catalysts for the reduction of nitroaromatic compounds and photo-oxidative degradation of toxic dyes. Nanoscale, 2014, 6(14): 7959. DOI PMID
[38]	BHATTACHARJEE A, AHMARUZZAMAN M. Green synthesis of 2D CuO nanoleaves (NLs) and its application for the reduction of p-nitrophenol. Materials Letters, 2015, 161: 79. DOI URL
[39]	TANG S, VONGEHR S, MENG X. Carbon spheres with controllable silver nanoparticle doping. Journal of Physical Chemistry C, 2010, 114(2): 977. DOI URL
[40]	YANG T, ZOU H Y, HUANG C Z. Synergetic catalytic effect of Cu_2-_xSe nanoparticles and reduced graphene oxide coembedded in electrospu n nanofibers for the reduction of a typical refractory organic compound. ACS Applied Materials & Interfaces, 2015, 7(28): 15447.
[41]	WANG Z, XU C, GAO G, et al. Facile synthesis of well-dispersed Pd-graphene nanohybrids and their catalytic properties in 4-nitrophenol reduction. RSC Advances, 2014, 4(26): 13644. DOI URL