Phân tích đặc tính cấu trúc và bề mặt vật liệu nanosilica biến tính, zeolite và đánh giá khả năng ứng dụng vật liệu để xử lý kháng sinh beta lactam

ĐẠI HỌC QUỐC GIA HÀ NỘI TRƯỜNG ĐẠI HỌC KHOA HỌC TỰ NHIÊN - Lê Thị Mai Anh PHÂN TÍCH ĐẶC TÍNH CẤU TRÚC VÀ BỀ MẶT VẬT LIỆU NANOSILICA BIẾN TÍNH, ZEOLITE VÀ ĐÁNH GIÁ KHẢ NĂNG ỨNG DỤNG VẬT LIỆU ĐỂ XỬ LÝ KHÁNG SINH BETA LACTAM LUẬN VĂN THẠC SĨ KHOA HỌC Hà Nội – 2020 ĐẠI HỌC QUỐC GIA HÀ NỘI TRƯỜNG ĐẠI HỌC KHOA HỌC TỰ NHIÊN - Lê Thị Mai Anh PHÂN TÍCH ĐẶC TÍNH CẤU TRÚC VÀ BỀ MẶT VẬT LIỆU NANOSILICA BIẾN TÍNH, ZEOLITE VÀ ĐÁNH GIÁ KHẢ NĂNG ỨNG DỤNG VẬT LIỆU ĐỂ XỬ LÝ KHÁNG SINH BETA LACTAM Chuyên ngành: Hóa phân tích Mã số: 8440112.03 LUẬN VĂN THẠC SĨ KHOA HỌC NGƯỜI HƯỚNG DẪN KHOA HỌC: TS Phạm Tiến Đức GS.TS Lê Thanh Sơn Hà Nội – 2020 LỜI CẢM ƠN Tơi xin bày tỏ lịng kính trọng biết ơn sâu sắc tới TS Phạm Tiến Đức ngƣời thầy giao đề tài, trực tiếp hƣớng dẫn bảo, tạo điều kiện thuận lợi giúp tơi hồn thành luận văn Tơi xin chân thành cảm ơn GS.TS Lê Thanh Sơn, thầy, mơn Hóa Phân tích nói riêng khoa Hóa học nói chung dạy dỗ, bảo động viên suốt thời gian học tập làm việc trƣờng Đại học Khoa học Tự nhiên Hà Nội Tơi cảm ơn phịng thí nghiệm, phịng ban chức khoa Hóa học – trƣờng Đại học Khoa học Tự nhiên tạo điều kiện giúp đỡ tơi q trình làm thí nghiệm Cuối cùng, muốn gửi lời cảm ơn đến gia đình, anh chị bạn học viên, em sinh viên Bộ mơn Hóa Phân tích động viên, khích lệ, tạo điều kiện giúp đỡ tơi suốt q trình thực hồn thành luận văn Hà Nội, ngày 22 tháng 11 năm 2020 Học viên Lê Thị Mai Anh i M M CL C MỞ ĐẦU CHƢƠNG 1: TỔNG QUAN 1.1 Giới thiệu kháng sinh họ β–lactam 1.1.1 Giới thiệu chung họ kháng sinh β–lactam 1.1.2 Kháng sinh Amoxicillin 1.2 Các phƣơng pháp phân tích kháng sinh họ β-lactam 1.2.1 Phƣơng pháp phổ hấp thụ phân tử (UV–Vis) 1.2.2 Phƣơng pháp phổ hồng ngoại FT-IR 1.2.3 Các phƣơng pháp phân tích điện hóa 1.2.4 Các phƣơng pháp sắc k lỏng 1.2.5 Phƣơng pháp điện di mao quản 10 1.3 Một số phƣơng pháp xử l kháng sinh họ β-lactam nƣớc 11 1.3.1 Phƣơng pháp sinh học 11 1.3.2 Phƣơng pháp oxi hóa tiên tiến 11 1.3.3 Phƣơng pháp hấp phụ 13 1.4 Giới thiệu vật liệu Silica 17 1.5 Giới thiệu vật liệu CeO2 vật liệu cấu trúc lõi vỏ CeO2@SiO2 18 CHƢƠNG 2: THỰC NGHIỆM 20 2.1 Đối tƣợng mục tiêu nghiên cứu 20 2.2 Nội dung nghiên cứu 20 2.3 Phƣơng pháp nghiên cứu 21 2.3.1 Phƣơng pháp đánh giá vật liệu 21 2.3.2 Phƣơng pháp quang phổ hấp thụ phân tử UV-Vis 22 2.3.3 Phƣơng pháp chế tạo vật liệu nanosilica, nano CeO2 vật liệu nano CeO2@SiO2 24 2.4 Hóa chất, thiết bị dụng cụ thí nghiệm 26 2.4.1 Hóa chất 26 2.4.2 Thiết bị 26 ii 2.4.3 Pha chế hóa chất 27 2.5 Quá trình xử l kháng sinh AMX 28 CHUƠNG 3: KẾT QUẢ NGHIÊN CỨU VÀ THẢO LUẬN 29 3.1 Đặc trƣng vật liệu nanosilica chế tạo từ vỏ trấu 29 3.2 Đặc trƣng vật liệu zeolite 30 3.3 Đặc trƣng vật liệu CeO2 CeO2@SiO2 chế tạo từ vỏ trấu 32 3.4 Xây dựng quy trình phân tích kháng sinh Amoxicillin phƣơng pháp quang phổ UV-Vis 36 3.4.1 Chọn bƣớc sóng đo phổ 36 3.4.2 Khảo sát khoảng tuyến tính 37 3.4.3 Xây dựng đƣờng chuẩn 37 3.4.4 Đánh giá phƣơng trình hồi quy đƣờng chuẩn 38 3.4.5 Giới hạn phát (LOD) giới hạn định lƣợng (LOQ) theo đƣờng chuẩn 38 3.5 Xử l kháng sinh AMX vật liệu hấp phụ khác 39 3.6 Khảo sát điều kiện hấp phụ xử l kháng sinh AMX CeO2@SiO2 40 3.6.1 Khảo sát thời gian hấp phụ 40 3.6.2 Khảo sát ảnh hƣởng pH 41 3.6.3 Ảnh hƣởng lƣợng chất hấp phụ tới hiệu suất xử l AMX 43 3.6.4 Khảo sát ảnh hƣởng nồng độ muối KCl 44 3.6.5 Hấp phụ đẳng nhiệt 45 3.6.6 Động học hấp phụ 47 3.7 Cơ chế hấp phụ AMX CeO2@SiO2 48 3.7.1 Đánh giá thay đổi nhóm chức bề mặt phổ hồng ngoại 48 3.7.2 Đánh giá thay đổi điện tích bề mặt vật liệu hấp phụ phƣơng pháp đo zeta 48 3.8 So sánh hiệu CeO2@SiO2 vật liệu khác đ xử l AMX 49 KẾT LUẬN 52 TÀI LIỆU THAM KHẢO 53 iii Tiếng Việt 53 Tiếng Anh 53 PH L C 59 iv DANH MỤC BẢNG Bảng 3.1 Diện tích bề mặt th tích mao quản zeolite SSZ-13 31 Bảng 3.2 Kết khảo sát hiệu suất xử l AMX theo thời gian 40 Bảng 3.3 Kết khảo sát hiệu suất xử l AMX pH khác 42 Bảng 3.4 Ảnh hƣởng muối tới khả xử l AMX 44 Bảng 3.5 Các thông số đƣờng hấp phụ đẳng nhiệt Amoxicillin (AMX) CeO2@SiO2 nồng độ KCl khác áp dụng mơ hình Langmuir, Freundlich mơ hình hai bƣớc hấp phụ 45 Bảng 3.6 Các thông số mơ hình động học hấp phụ AMX CeO2@SiO2 47 Bảng 3.7 Dung lƣợng hấp phụ hiệu suất xử l Amoxicillin sử dụng CeO2@SiO2 chất hấp thụ khác 50 v DANH MỤC HÌNH Hình 1.1 Cấu trúc hóa học kháng sinh amoxicillin Hình 1.2 Mơ cấu trúc silica 17 Hình 1.3 Các dạng liên kết nhóm Si-O bề mặt silica 18 Hình 2.1 Ảnh chụp vỏ trấu (a), vỏ trấu nghiền thành bột (b) vật liệu nanosilica đƣợc chế tạo thành công từ vỏ trấu (c) 25 Hình 2.2 Ảnh chụp vật liệu nano CeO2 chế tạo phịng thí nghiệm 25 Hình 2.3 Ảnh chụp vật liệu CeO2@SiO2 chế tạo phịng thí nghiệm 26 Hình 3.1 Giản đồ XRD vật liệu nanosilica chế tạo từ vỏ trấu 29 Hình 3.2 Phổ hồng ngoại FT-IR vật liệu nanosilica chế tạo từ vỏ trấu 29 Hình 3.3 Ảnh SEM vật liệu nanosilica chế tạo từ vỏ trấu 30 Hình 3.4 Giản đồ XRD vật liệu SSZ-13 30 Hình 3.5 Đƣờng đẳng nhiệt hấp phụ N2 SSZ-13 -196 31 Hình 3.6 Hình ảnh SEM mẫu SSZ-13 32 Hình 3.7 Giản đồ XRD vật liệu CeO2 (a) CeO2@SiO2 (b) 32 Hình 3.8 Phổ hồng ngoại FT-IR vật liệu CeO2 (a) CeO2@SiO2 (b) 33 Hình 3.9 Đƣờng đẳng nhiệt hấp phụ giải hấp phụ N2 CeO2 (a) CeO2@SiO2 (b) 34 Hình 3.10 Ảnh SEM CeO2 (a) CeO2@SiO2 (b) 35 Hình 3.11 Thế ζ vật liệu CeO2 CeO2@SiO2 giá trị pH khác điện phân KCl mM 35 Hình 3.12 Phổ UV-Vis kháng sinh AMX 36 Hình 3.13 Đồ thị khảo sát khoảng tuyến tính kháng sinh AMX 37 Hình 3.14 Đƣờng chuẩn xác định AMX 38 Hình 3.15 Hiệu suất xử l kháng sinh AMX vật liệu SiO 2, CeO2 CeO2@SiO2 39 Hình 3.16 Ảnh hƣởng thời gian hấp phụ tới khả xử lí kháng sinh AMX sử dụng vật liệu CeO2@SiO2 41 vi Hình 3.17 Ảnh hƣởng pH đến hiệu suất xử l AMX sử dụng vật liệu CeO2@SiO2 42 Hình 3.18 Ảnh hƣởng lƣợng chất hấp phụ tới hiệu suất xử l AMX sử dụng vật liệu CeO2@SiO2 43 Hình 3.19 Ảnh hƣởng muối KCl đến khả xử l AMX 44 Hình 3.20 Đƣờng hấp phụ đẳng nhiệt AMX CeO2@SiO2 nồng độ KCl khác Các m thực nghiệm đƣờng đƣợc mô tả mơ hình hai bƣớc hấp phụ 46 Hình 3.21 Phổ FT-IR CeO2@SiO2 sau hấp phụ AMX 48 Hình 3.22 Thế ζ CeO2@SiO2 trƣớc sau hấp phụ AMX pH 49 Hình 3.23 Hình ảnh minh họa hấp phụ AMX bề mặt CeO2@SiO2 49 Hình 3.24 Hiệu suất xử l kháng sinh AMX sử dụng vật liệu CeO2@SiO2 sau bốn lần tái sử dụng…………………………………………………… … 51 vii CÁC KÝ HIỆU VIẾT TẮT Ký hiệu Tiếng Anh Tiếng việt AMX Amoxicillin Kháng sinh Amoxicillin BOD Biochemical Oxygen Demand Nhu cầu oxy sinh hoá COD Chemical Oxygen Demand Nhu cầu oxy hóa học FT - IR Fourier transform infrared Phổ hồng ngoại biến đổi spectroscopy Fourier LOD Limit Of Detection Giới hạn phát LOQ Limit Of Quantity Giới hạn định lƣợng MWCNT Multi-Walled Carbon Ống nano carbon đa vách Nanotube ngăn SD Standard Deviation Độ lệch chuẩn SEM Scanning Electron Microscope Kính hi n vi điện tử quét TEM Transmission electron Kính hi n vi điện tử truyền microscopy qua UV – Vis Ultraviolet Visble Phổ hấp thụ phân tử UV-Vis XRD X-ray Diffraction Nhiễu xạ tia X viii KẾT LUẬN Luận văn nghiên cứu đặc tính hấp phụ kháng sinh β - lactam AMX vật liệu hấp phụ nanosilca, zeolite, CeO2 CeO2@SiO2 chế tạo từ vỏ trấu Kết kết thu đƣợc nhƣ sau: - Vật liệu nanosilica, zeolite, nano CeO2 CeO2@SiO2 đƣợc chế tạo thành cơng đƣợc xác định đặc tính cấu trúc, bề mặt phƣơng pháp XRD, FTIR, SEM, BET đo zeta - Vật liệu CeO2 CeO2@SiO2 phù hợp đ xử l kháng sinh AMX vật liệu zeolite, SiO2 Hiệu suất xử l AMX vật liệu CeO2@SiO2 cao so với sử dụng vật liệu CeO2 cao nhiều so với SiO2 - Điều kiện hấp phụ tối ƣu xử l AMX vật liệu CeO2@SiO2: thời gian hấp phụ 120 phút, pH= 3, lƣợng vật liệu mg/mL - Hấp phụ kháng sinh AMX vật liệu CeO2@SiO2 chủ yếu lực tƣơng tác tĩnh điện - Vật liệu CeO2@SiO2 có khả tái sử dụng tốt, sau lần tái sử dụng hiệu suất xử l AMX cao 75% Công trình nghiên cứu luận văn chứng minh vật liêu nano cấu trúc lõi vỏ CeO2@SiO2 với phần lõi nanosilica chế tạo từ trấu vật liệu hấp phụ với hiệu cao đ xử l kháng sinh beta lactam môi trƣờng nƣớc 52 TÀI LIỆU THAM KHẢO Tiếng Việt Trần Thúc Bình (2015),“Xác định đồng thời AMX Kali clavulanate dƣợc phẩm phƣơng pháp trắc quang Chemometrics”, Tạp chí phân tích Hóa, Lý 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Zhong, J B et al (2014)“Fabrication and Catalytic Performance of SiO2-ZnO Composite Photocatalyst”, Synthesis and Reactivity in Inorganic, MetalOrganic and Nano-Metal Chemistry, 44(8), pp 1203–1207 54 Zones, S (1991)“Conversion of faujasites to high-silica chabazite SSZ-13 in the presence of N,N,N-trimethyl-1-adamantammonium iodide”, Journal of the Chemical Society, Faraday Transactions, 87(22), pp 3709–3716 58 PHỤ LỤC Phụ lục Hình Phổ FT- IR kháng sinh AMO Phụ lục Phổ FT-IR kháng sinh AMX 59 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx Vietnam Journal of Catalysis and Adsorption Tạp chí xúc tác hấp phụ Việt Nam http://chemeng.hust.edu.vn/jca/ ADSORPTION CHARACTERISTICS OF AMOXICILLIN ANTIBIOTIC ON CeO2-COATED SiO2 NANOMATERIALS Thi Mai Anh Le1, Thi My Quynh Pham1, The Dung Nguyen1,*, Tien Duc Pham1,* Faculty of Chemistry, University of Science, Vietnam National University – Hanoi, 19 Le Thanh Tong, Hoan Kiem, Hanoi 100000, Vietnam *Email: nguyentd@hus.edu.vn (T.D Nguyen), tienducpham@hus.edu.vn (T.D Pham) ARTICLE INFO ABSTRACT Received: December 11, 2020 Accepted: January 08, 2021 This study investigated adsorption of beta-lactam antibiotic Amoxicillin (AMX) on a new material of cerium oxide-coated nanosilica (CeO2-coated SiO2) The CeO2-coated SiO2 based on rice husk, was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) Adsorption behaviors of AMX on CeO2-coated SiO2 at different pH and ionic strength were thoroughly studied The highest removal of AMX using CeO 2-coated SiO2 reached 99.26 % at pH while the maximum adsorption capacity was found to be greater than 11.0 mg/g Adsorption isotherms of AMX on CeO2coated SiO2 at different ionic strength were in accordance with Freundlich model Adsorption of amphoteric AMX species on CeO2-coated SiO2 increased with a decrease of salt concentration indicating that adsorption was controlled by both electrostatic and non-electrostatic interactions Keywords: Adsorption, CeO2coated SiO2, Nanomaterials, Amoxicillin, Rice husk Introduction Metal oxides are important materials that are widely used in chemical engineering, such as adsorption technology Cerium oxide (CeO2) is high performance adsorbent for for removal of various pollutants [1-3] However, due to high cost material, CeO2 is not common metal for environmental remediation On the one hand, silica (SiO2) is a very common material for water and wastewater treatment[4] The evident disadvantage of SiO2 is easily dissolved in basic media Recently, the material is based on the combination between CeO2 and SiO2 to form a new material as CeO2-coated SiO2 attracted intense studies [5,6] Different methods have been investigated to synthesize CeO2-coated SiO2,, for example chemical precipitation [1,6], soft fabrication in the presence of surface active agent [7], sol-gel [5], solvothermal [8] and dispersion with impregnation [9] It implies that the chemical precipitation is the one of the simplest method to fabricate CeO2-coated SiO2 In order to decrease the price of material, SiO2 should be synthesized from agricultural sub-product such as rice husk Nano-SiO2 is easily produced from rice husk with simple procedure due to high amount of silica in its product [4] To the best our knowledge, the CeO2coated SiO2 material based on SiO2 rice husk has not been studied Amoxicillin (AMX) is one of the most popular beta lactam antibiotic that causes a serious problem in antibiotic resistance genes [10] [11] Among various techniques for removal of antibiotic, adsorption is known as an effective technique to remove antibiotic in water enviroment with high efficiency This technique is 60 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx also suitable for developing countries by using lowcost adsorbents such as minerals, industrial wastes or agricultural sub-product In this work, for the first time, we investigated the adsorption of AMX on synthesized CeO2-coated SiO2 nanomaterials The CeO2-coated SiO2 based on rice husk was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Scanning electron microscopy (SEM) Adsorption of AMX at different pH and ionic strength was thoroughly studied Adsorption mechanism was also studied on the basis of adsorption isotherm and the change in surface charge of CeO2-coated SiO2 after AMX adsorption Experimental Materials Amoxicillin trihydrate with purity 98% (HPLC grade) was purchased from Tokyo Chemical Industry (Tokyo, Japan) The chemical structure of AMX is indicated in Figure Cerium (III) nitrate hexahydrate (99 %) was purchased from Shanghai Zhanyun Chemical Nanosilica (SiO2) was fabricatd from rice husk according to our previously published papers [4,12] Ionic strength and pH were studied by using KCl with addition of HCl and KOH (p.A, Merck, Germany) All solutions which were prepared by pure water from ultrapure water system (Labconco, USA) with a resistivity of 18.2 MΩcm The pH of solution was monitored by using an HI 2215 pH meter (Hanna, USA) Other chemicals with analytical grade were supplied from Merck sulfuric acid (0.2M H2SO4) was used before washing with ultrapure water Finally, nanosilica particles were re-heated at 800 °C for 24 h and then cooled to room temperature to obtain SiO2 powder Synthesis of CeO2-coated SiO2 based on rice husk The procedure was followed Dhmees et al [1] with the modifications First of all, 2.0 g SiO2 fabricated from was dispersed in 100 mL ethanol A 4.0 g Ce(NO3)3 was added to SiO2 suspension The pH was slowly adjusted to 10 by M KOH After 2h reaction, the yellow precipitation was separated by centrifuging and washed by pure water The sample was heated for 2h before calcinating at 600 ℃ for 3h Finally, the sample was cooled to room temperature in a desiccator Characterization methods The CeO2-coated SiO2 was characterized by XRD, FT-IR and SEM measurements The XRD pattern was conducted on a Bruker D8 Advance X-ray Diffactometer The FT-IR spectra were recorded with an Affinity-1S spectrometer (Shimadzu, Kyoto, Japan) while SEM and TEM images were collected by Hitachi S4800, Japan and JEM- 2100, (Jeol, Japan) To evaluate the change in surface charge after adsorption, the ζ potential measurements were used The ζ potential was calculated from electrophoretic mobility with Smoluchowski’s equation ζ= (1) where ζ is the ζ potential (mV), ue is the electrophoretic mobility (µm.cm/sV), η is the dynamic viscosity of the liquid (mPa.s), εrs is the relative permittivity constant of the electrolyte solution, and ε0 -12 is the electric permittivity of the vacuum (8.854 x 10 F/m) Adsorption studies All adsorption experiments were conducted in in 15mL Fancol tubes at room temperature controlled by an air conditioner at 25 ± 2℃ Fig 1: Structure of beta lactam Amoxicillin (AMX) Synthesis of nano SiO2 from rice husk Nanosilica was synthesized from rice husk according to our previously published paper, [[12] A 80 g of milled rice husk was placed in a L beaker containing 386 g of ultrapure water and 14 g of concentrated H2SO4 and stirred for at least h at 120 °C After that, the pretreated rice husk was washed with ultrapure water until neutral pH was reached Then, the rice husk was dried at 110 °C for h and calcined in a thermal furnace at 800 °C for 12 h to obtain nanosilica To purify nanosilica, diluted The influence of pH and ionic strength on AMX adsorption were studied The UV-Vis spectroscopy using a spectrophotometer (UV-1650 PC, Shimadzu, Japan) was used to determine all AMX concentrations at a wavelength of 229 nm The removal of AMX using CeO2-coated SiO2 was calculated by Equation(2) (2) 61 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx where Ci (mg/L), Ce (mg/L) and Cf (mg/L) are the initial, the equilibrium and the final concentrations of AMX, respectively while m (g/L) is adsorbent dosage The adsorption isotherm is fitted by Freundlich model [13]: Lnqe = LnKF LnCe + (3) n−1 n where KF (mg L /g) is the Freundlich constant, qe is adsorption capacity and 1/nF is the adsorption intensity Fig 3: FT-IR spectra of CeO2-coated SiO2 nanomaterials Results and discussion Characterizations of CeO2-coated SiO2 based on rice husk The synthesized CeO2-coated SiO2 was characterized by XRD, FTIR, and SEM The SEM image of CeO2-coated SiO2 in Figure show that CeO2-coated SiO2 has the average diameter of CeO2-coated SiO2 is about 30 nm The XRD pattern of CeO2-coated SiO2 is indicated in Figure AnhPT 150 140 130 120 d=4.045 110 100 d=3.122 Lin (Cps) 90 80 70 60 d=1.631 30 d=2.486 d=2.702 40 d=1.912 50 Fig 4: SEM image of CeO2-coated SiO2 nanomaterials d=1.240 20 10 10 20 30 40 50 60 70 2-Theta - Scale Figure shows the TEM image of CeO2-coated SiO2 has cubic with the diameter of CeO2-coated SiO2 is aroundt 30 ± 10 nm 80 AnhPT - File: AnhPT.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 80.000 ° - Step: 0.020 ° - Step time: s - Temp.: 25 °C (Room) - Time Started: s - 2-Theta: 2.000 ° - Theta: 1.000 ° - Chi: 0.00 ° - Phi: 0.00 ° - Aux1: 00-034-0394 (*) - Cerianite-(Ce), syn - CeO2 - Y: 62.63 % - d x by: - WL: 1.5406 - Cubic - a 5.41134 - b 5.41134 - c 5.41134 - alpha 90.000 - beta 90.000 - gamma 90.000 - Face-centered - Fm-3m (225) - - 158.458 - F1 00-004-0379 (D) - Cristobalite - SiO2 - Y: 100.00 % - d x by: - WL: 1.5406 - Tetragonal - a 4.97300 - b 4.97300 - c 6.95000 - alpha 90.000 - beta 90.000 - gamma 90.000 - Primitive - P41212 (92) - - 171.879 - F30= 16(0 Fig 2: XRD pattern of CeO2-coated SiO2 nanomaterials Figure shows that XRD pattern of CeO2-coated SiO2 appearred the specific peaks at 2θ 21.83°, 28.33°, 31.29°, and 36.00° for Cristobaline [14], while the peaks occurred at 28.6° , 33.1° , 47.5° and 56.4° indicates the structure of CeO2 [6] The CeO2 was evident on SiO2 surface due to the appearances of both specific peaks of SiO2 and CeO2 with strong intensities Figure shows the FT-IR spectrum of CeO2-coated -1 -1 SiO2 The bands at 451.34 cm and 798.53 cm assigned for the Si-O bending and stretching vibrations of SiO2, respectively Furthermore, the Ce–O stretching appearred at the peaks of 451.34 [7] The results of FT-IR spectrum confirmed the specific vibration of CeO2-coated SiO2 Fig 5: TEM image of CeO2-coated SiO2 nanomaterials Based on XRD, FT-IR and SEM and TEM results, we indicate that CeO2-coated SiO2 nanomaterials successfully synthesized in the laboratory Adsorption of nanomaterials AMX on CeO2-coated SiO2 62 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx Effect of pH The pH of solution is one of the most effective parameter on AMX adsorption because pH induces the surface charge of CeO2-coated SiO2 nanomaterials and the charging AMX species Figure shows that AMX removal using CeO2-coated SiO2 decreased with increasing pH that is similar to AMX adsorption on activated carbon nanoparticles synthesized from vine wood [15] However at pH 3, a slighly decrease of AMX removal because of the dissolution of material at high acid media When increasing pH from to 10, the AMX removal reduced due to the decrease of positively charged CeO2-coated SiO2 surface while AMX occurred with amphoteric containing both negative and positive species The removal of AMX decreased dramatically at pH > 6.0 at which the charge reversal of CeO2-coated SiO2 was taken place while the AMX changed to negative form Therefore, pH is the optimum solution condition and to be kept further study Fig 7: The AMX removal using CeO2-coated SiO2 CeO2-coated SiO2 and SiO2 adsorbents (Ci,,AMX = 2.5 mg/L, pH 4, adsorbent dosage mg/mL, and mM KCl) Error bars show standard deviations of three replicates Effect of ionic strength The effect of ionic strength is clearly observed on the adsorption isotherms at different salt concentrations (Figure 6) Figure shows that the adsorption of AMX on CeO2coated SiO2 increased with decreasing KCl concentrations from to 100 mM The Freundlich model can fit the isotherms well with R > 0.971 that is much better than Langmuir isotherms with R < 0.820 In other words, adsorption of AMX on CeO2-coated SiO2 followed by multi-layer than mono-layer (nF >2.2) The maximum adsorption capacity of AMX on CeO2coated SiO2 was found to be 11 mg/g that was higher than using other adsorbent [4] Fig 6: Effect of pH to AMX removal using CeO2-coated SiO2 nanomaterials (Ci,,AMX = 2.5 mg/L, adsorbent dosage 5mg/mL, and mM KCl) Error bars show standard deviations of three replicates In order to emphasize the efficiency of CeO2-coated SiO2 in the AMX removal, we compare AMX removal using the SiO2, CeO2, and CeO2-coated SiO2 (Figure 7) As can be seen in Figure 7, the AMX removal using CeO2-coated SiO2 was higher than CeO2 and much higher than SiO2 It implies that CeO2-coated SiO2 is the best adsorbent for AMX removal The CeO2 covering SiO2 is necessary to enhance the removal efficiency Fig 8: Adsorption isotherms of AMX on CeO2-coated SiO2 nanomaterials at different KCl concentrations fitted by the Freundlich model Adsorption mechanisms Adsorption mechanism of AMX on CeO2-coated SiO2 is suggested based on adsorption isotherms and the surface charge change by ζ potential measurements 63 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx The surface measurement charge change by ζ potential To determine the change in surface charge of CeO2coated SiO2 after AMX adsorption, we measured the ζ potential using Smoluchowski’s equation [16] The ζ potentials of CeO2-coated SiO2 before and after AMX adsorption at pH in mM KCl are indicated in Figure spectroscopy (FTIR), and Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) The nanometer-sized CeO2-coated SiO2 with average diameter was approximately 30 nm The optimum solution conditions of AMX nano CeO2-coated SiO2 was found to be pH 4.0 and mM KCl Adsorption isotherms of AMX onto nano CeO2-coated SiO2 was well represented by Freundlich model Based on adsorption isotherm and the change in surface charge by ζ potential measurment and FT-IR spectra of CeO2coated SiO2 after AMX adsorption, we indicate that AMX adsorption on nano CeO2-coated SiO2 was controlled by both electrostatic and non-electrostatic interactions in which electrostatic one was dominant Acknowledgement This research is funded by the Vietnam National University, Hanoi (VNU) under project number QG.20.22 References Fig 9: The ζ potential of CeO2-coated SiO2 before and after AMX adsorption at pH in mM KCl Figure9 shows that at pH 4, after AMX adsorption the positive charge of CeO2-coated SiO2 decreased At pH 4, adsorption of AMX was highest that induced the significant decrease in surface charge Although, at pH 4, the zitterionic form of AMX is dominated because this pH is greater than pKa1 of AMX (2.67), the adsorption is higher Other interactions such as hydrogen bonding, hydrophobic interactions may induce the AMX adsorption but the main driving force is electrostatic attraction between negative AMX species and positvely charged CeO2-coated SiO2 The results were in good agreement with FT-IR spectra of CeO2-coated SiO2 after AMX adsorption (not shown here) After AMX adsorption, the wavenumber at about -1 1400 cm for –COOH enhanced while the assigned -1 peak at 1000 cm for –NH vibration did not observe The change in surface charge by ζ potential and surface vibration group change by FT-IR demonstrate that AMX adsorption on CeO2-coated SiO2 was mainly controlled by electrostatic interaction Conclusion We have studied adsorption of Amoxicillin (AMX) on nano CeO2-coated SiO2 Nano CeO2-coated SiO2 which was fabricated by chemical precipitation method based on rice husk, was characterized by X-ray diffraction (XRD), Fourier-transform infrared Dhmees, A.S.; Rashad, A.M.; Eliwa, A.A.; Zawrah, M.F (2019), "Preparation and characterization of nano SiO2@CeO2 extracted from blast furnace slag 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solutions using activated carbon nanoparticles prepared from vine wood", Journal of Water Process Engineering, 1, 64-73 16 Delgado, A.V.; González-Caballero, F.; Hunter, R.J.; Koopal, L.K.; Lyklema, J (2007), "Measurement and interpretation of electrokinetic phenomena", Journal of Colloid and Interface Science, 309, 194-224 65 Vietnam Journal of Catalysis and Adsorption, – issue (2021) xxx-xxx HỘI KHCN XÚC TÁC VÀ HẤP PH VIỆT NAM TẠP CHÍ XÚC TÁC VÀ HẤP PHỤ VIỆT NAM Số: 47/GXN-TCXTHPVN CỘNG HÒA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập - Tự - Hạnh phúc Hà Nội, ngày 08 tháng 01 năm 2021 GIẤY XÁC NHẬN Ban biên tập Tạp chí Xúc tác Hấp phụ Việt Nam nhận đƣợc thảo báo: “ADSORPTION CHARACTERISTICS OF AMOXICILLIN ANTIBIOTIC ON CeO2-COATED SiO2 NANOMATERIALS” Nhóm tác giả: Thi Mai Anh Le, Thi My Quynh Pham, The Dung Nguyen,*, Tien Duc Pham,* Địa chỉ: Faculty of Chemistry, University of Science, Vietnam National University – Hanoi, 19 Le Thanh Tong, Hoan Kiem, Hanoi 100000, Vietnam *Email: nguyentd@hus.edu.vn (T.D Nguyen), tienducpham@hus.edu.vn (T.D Pham) Bài báo đƣợc phản biện nghĩa khoa học, khả ứng dụng, chất lƣợng học thuật đáp ứng yêu cầu Ban biên tập Tạp chí Xúc tác Hấp phụ Việt Nam đồng cho đăng báo vào năm 2021 Trân trọng 66 ... Thị Mai Anh PHÂN TÍCH ĐẶC TÍNH CẤU TRÚC VÀ BỀ MẶT VẬT LIỆU NANOSILICA BIẾN TÍNH, ZEOLITE VÀ ĐÁNH GIÁ KHẢ NĂNG ỨNG DỤNG VẬT LIỆU ĐỂ XỬ LÝ KHÁNG SINH BETA LACTAM Chuyên ngành: Hóa phân tích Mã số:... cứu: ? ?Phân tích đặc tính cấu trúc bề mặt vật liệu nanosilica biến tính, zeolite đánh giá khả ứng dụng vật liệu để xử lý kháng sinh beta lactam? ?? 2 CHƢƠNG 1: TỔNG QUAN 1.1 Giới thiệu kháng sinh. .. tử kháng sinh AMX Khảo sát khoảng tuyến tính, xây dựng đƣờng chuẩn xác định kháng sinh AMX - Nghiên cứu so sánh hiệu suất xử l kháng sinh AMX vật liệu zeolite, nanosilica không biến tính, vật liệu