粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(II)与催化降解有机污染物

doi:10.15541/jim20230209

无机材料学报 ›› 2023, Vol. 38 ›› Issue (11): 1281-1291.DOI: 10.15541/jim20230209

粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(II)与催化降解有机污染物

汤亚¹^,²(), 孙盛睿², 樊佳¹^,², 杨庆峰³, 董满江², 寇佳慧¹(), 刘阳桥²()

1.南京工业大学材料科学与工程学院, 材料化学工程国家重点实验室, 南京210009
2.中国科学院上海硅酸盐研究所, 上海200050
3.中国科学院上海高等研究院, 上海201210

收稿日期:2023-04-28 修回日期:2023-05-29 出版日期:2023-06-01 网络出版日期:2023-06-01
通讯作者: 刘阳桥, 研究员. E-mail: yqliu@mail.sic.ac.cn;
寇佳慧, 教授. E-mail: koujiahui@163.com
作者简介:汤亚(1998-), 男, 硕士研究生. E-mail: tangya153@163.com
基金资助:
国家自然科学基金(51878647);国家自然科学基金(52272082);太仓市基础研究计划(TC2020JC08);江苏省高等学校重点学科建设(PAPD)

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

TANG Ya¹^,²(), SUN Shengrui², FAN Jia¹^,², YANG Qingfeng³, DONG Manjiang², KOU Jiahui¹(), LIU Yangqiao²()

1. State Key Laboratory of Materials-Oriented Chemical Engineering, College of Materials Science and Engineering, Nanjing Tech University, Nanjing 210009, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China

Received:2023-04-28 Revised:2023-05-29 Published:2023-06-01 Online:2023-06-01
Contact: LIU Yangqiao, professor. E-mail: yqliu@mail.sic.ac.cn;
KOU Jiahui, professor. E-mail: koujiahui@163.com
About author:About author: TANG Ya (1998-), male, Master candidate. E-mail: tangya153@163.com
Supported by:
National Natural Science Foundation of China(51878647);National Natural Science Foundation of China(52272082);Taicang Basic Research Program(TC2020JC08);Jiangsu Higher Education Institutions(PAPD)

摘要/Abstract

摘要：

随着工业的快速发展, 相关制造领域排放的污水重金属铜离子污染愈发严重。与此同时, 催化领域对铜金属资源的需求却不断增加。本研究利用粉煤灰和改性剂聚乙烯亚胺(PEI)制备了低成本改性水合硅酸钙(PCSH), 用于吸附水溶液中的铜离子(Cu(II)), 并进一步碱处理固定于表面的Cu(II), 形成铜基活性材料用于有机污染物的催化降解。相比于未改性的样品(CSH), PCSH对Cu(II)的饱和吸附容量提高100%, 高达588 mg/g。研究发现, 这主要是因为添加PEI有利于形成较大的比表面积、优良的孔隙结构以及Cu(II)与-NH₂之间的强络合。从PCSH获得的铜基催化剂呈现纺锤形多孔形貌, 作为催化剂分别用于活化过氧硫酸氢钾(PMS)氧化降解罗丹明B(RhB)和活化硼氢化钠(NaBH₄)还原降解4-硝基苯酚(4-NP), 速率常数达到0.7135 /min (pH (7.0±0.3); [RhB]= 20 mg/L; [PMS]= 0.12 g/L; [催化剂]= 0.8 g/L)和11.47×10^-3 /s (pH (11.0±0.3); [4-NP]= 10^-4 mol/L; [NaBH₄]= 5×10^-3 mol/L; [催化剂]= 0.167 g/L), 是CSH催化剂体系的20和19倍。本工作利用固体废弃物粉煤灰实现了水溶液中铜元素的再利用, 为水中污染物的有效处理和利用提供了新启示。

关键词: 粉煤灰, 水合硅酸钙, 铜离子吸附, 聚乙烯亚胺, 过氧硫酸氢钾

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

中图分类号:

X522

汤亚, 孙盛睿, 樊佳, 杨庆峰, 董满江, 寇佳慧, 刘阳桥. 粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(II)与催化降解有机污染物[J]. 无机材料学报, 2023, 38(11): 1281-1291.

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.

图/表 18

图1 CSH与PCSH的(a) XRD图谱, (b) FT-IR图谱以及(c) N2吸附脱附曲线

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

图2 (a, b) CSH与 (c, d) PCSH的不同放大倍率SEM照片

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

图3 样品吸附性能表征

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)

图4 吸附Cu后样品的表征

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

图5 (a) CSH-Cu, (b) PCSH-Cu, (c) CSH-Cu-c, (d) PCSH- Cu-c的SEM照片

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

图6 CSH-Cu-c与PCSH-Cu-c的(a) XRD和(b) FT-IR图谱

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

图7 CSH-Cu-c和PCSH-Cu-c催化PMS降解RhB的性能

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

表1 不同材料催化PMS降解RhB的速率常数(k)

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

图8 样品表面元素和化学状态表征

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

图9 PCSH-Cu-c自由基捕获试验

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

图10 4-NP剩余浓度随时间的变化曲线

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

表2 不同材料催化NaBH4降解4-NP的速率常数(k)

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

图S1 CSH的EDS分析

Fig. S1 EDS analyses of CSH

图S2 PCSH的EDS分析

Fig. S2 EDS analysis of PCSH

图S3 CSH与PCSH在(a) Langmuir模型和(b) Freundlich模型中的吸附等温线拟合

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

图S4 PCSH-Cu的EDS分析

Fig. S4 EDS analyses of PCSH-Cu

表S1 Langmuir和Freundlich等温线拟合参数

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

表S2 文献中报道的各种吸附剂对Cu(II)的最大吸附能力比较

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

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粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(II)与催化降解有机污染物

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

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