Innovative procedure for incorporating nanomaterial onto cellulose membranes and its application in color removal from water = nghiên cứu tổng hợp vật liệu nano trên màng xenllulo và ứng dụng xử lý màu trong nước

TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Innovative procedure for incorporating nanomaterial onto cellulose membranes and its application in color removal from water Dương, Thị Lương Ngành Quản lý tài nguyên môi trường Giảng viên hướng dẫn: Trần Lệ Minh HÀ NỘI, 2021 Acknowledgement My research would not be completed without the guidance, support and generous contribution of many It is a pleasure to thank those who made this possible First of all, I would like to express my endless thanks to the RoHan - Rostock Hanoi DAAD SDG Graduate School, which had provided me a Master Research Exchange Course - a precious learning opportunity at the University of Rostock, Germany I would like to offer my sincere appreciation to project coordinators, Prof Dr Le Minh Thang, Dr Dirk Hollmann, and Dr Esteban Mejia, who enthusiastically guided and helped me during the process of studying, researching and completing this thesis I cannot express enough thanks to my supervisors, Dr Dirk Hollmann of Institute for Chemistry at Rostock University, Dr Nguyen Ngoc Mai of School of Chemical Engineering and Dr Tran Le Minh at School of Environmental Science and Technology, Hanoi University of Science and Technology (HUST) During my research, Dr Dirk Hollmann and Dr Nguyen Ngoc Mai gave me their tireless guidance with laboratory skills as well as helpful advices for my troubles with high responsibility Dr Tran Le Minh is a big inspiration to me, she always encourages me and provide me with valuable comments I am also grateful to my teachers at School of the Environmental Science and Technology– HUST, who always facilitate me to accomplish my thesis and all other subjects on schedule Finally, my great gratitude is for my family and my friends who always believed and encouraged me so much during my years of study Thank you! Author, Duong Thi Luong i Declaration I hereby declare that this thesis was done by me in the training program of the Hanoi University of Science and Technology Datas and results in the thesis are truthful and have never been published I am completely responsible for the content of the thesis Author ii Summary of thesis Nowadays, the issue of color in wastewater easily noticed by other people The release of this colored wastewater into the environment can have negative impacts on the aquatic ecosystem One of the main concerns is the reduction of lightradiation penetration into the water, which can hinder the photosynthetic activity and thus alter the ecological balance of flora and fauna Hence, the treatment of colored water aims to enforce compliance with strict regulations on the water quality and thus to protect human health The current popular treatment methods are chemical/physical, chemical (conventional and advanced), electrochemical and biological processes Among these, membrane technology is a new method that has been attracting attention in recent years However, conventional membranes mainly separate pollutants without ability of degradation A potential method to enhance treatment performance of membrane technology is to immobilize photocatalysts into cellulose membranes, which can reduce the cost of separation after treatment, provide great potential for reusing and make use of cellulose as abundant, renewable, environmentally friendly resource On the other hand, the presence of photocatalytic nanomaterials offers strong oxidation capacity, and photodegradation under light irradiations In this research, a composite of nanomaterials and cellulose membranes were fabricated and its application in color removal from water was investigated Research objectives, subjects, scope and methods Research objectives: - Synthesize nanomaterials-cellulose membranes from cellulose powder and photocatalysts (Au/TiO2-P25 and Au/sg-C3N4) - Survey the photodegradation of obtained materials via the photodegradation of colored solutions under UV-Vis and visible irradiation Research subjects: - Nanomaterial-cellulose membranes from the combination of cellulose membranes and photocatalysts (Au/TiO2 and Au/sg-C3N4) - Methylene blue as a colored solution for photodegradation evaluation under ultraviolet-visible and visible irradiation Research scope: In laboratory of University of Rostock, 18051 Rostock, Germany - Department of Life, Light and Matter, Interdisciplinary Faculty, University of Rostock, Albert-Einstein-Str 25 - Institute for Chemistry, University of Rostock, Albert-Einstein-Str.3a Research methods: Document collection, experimental studies, analytical, statistical, data processing and graphic methods were used iii Summary and conclusion A new procedure was enclosing to synthesize new nanomaterial-cellulose composite membranes which can be utilized in advanced photocatalytic membrane technology Inorganic (Au/TiO2-P25) and organic (Au/sg-C3N4) photocatalysts can be easily incorporated into cellulose membranes The nanomaterials were immobilized into the membranes and showed homogeneous distribution ICP analysis showed that the photocatalysts can be inserted in the cellulose film with little material loss An agglomeration of titanium oxide and cellulose as well as randomly distributed Au particles of sizes between and 15 nm were be observed by TEM The presence of photocatalysts had no effect on cellulose structure, demonstrated by FT-IR and XRD In terms of photodegradation of methylene blue, nanomaterial-cellulose membranes with Au/sg-CN exhibited a better photodegradation in comparison to those with Au/ TiO2-P25, especially under visible irradiation For instance, CellCN30 showed 91.2% of MB photodegradation while it was 56,6% from CellP30 under visible irradiation in batch reactor With UV-Vis both composites show high conversion at 92.8% In consideration of the decomposition stems from absorption of cellulose substrate, negative charges from OH- on cellulose membrane surface had a strong connection with positive charge dyes, hence, it indicates that a large proportion of decomposition stems from photocatalysis The excellent absorbance capacity of cellulose increased the time at the membrane and thus enabling a high photocatalytic conversion This procedure is a straightforward environmentally friendly methodology to produce nanomaterialcellulose composites In this work, nanomaterial-cellulose composite membranes was successfully fabricated from environmentally friendly and reusable materials, contributing to the applications of photocatalytic membrane technology in water treatment Author iv Table of content Acknowledgement i Declaration ii List of Figures vii List of Tables ix List of Symbols and Abbreviations x INTRODUCTION 1 LITERATURE REVIEW 1.1 Color pollution in water 1.1.1 Sources of color pollution 1.1.2 Status of color pollution in water 1.1.3 Effects of color pollution in water on environment and human health 1.2 Treatments for color removal 1.2.1 Chemical/Physical processes 1.2.2 Chemical oxidation processes 10 1.2.3 Electrochemical processes 13 1.2.4 Biological processes 13 1.3 Color removal from water by nanomaterial-cellulose membranes 14 1.3.1 Basis for methods of color removal in water 14 1.3.2 Mechanism for color treatment in water 16 1.4 Researches on nanomaterial-cellulose membranes 20 1.4.1 Researches on nanomaterial-cellulose membranes fabrication 20 1.4.2 Application of nanomaterial-cellulose membranes 24 RESEARCH METHODS AND EXPERIMMENTAL PROCESSES 26 2.1 Chemicals and apparatus 26 2.1.1 Chemicals 26 2.1.2 Apparatus 26 2.2 Research methods 26 2.3 Experimental processes 27 The procedure of the research was shown in the below diagram: 27 2.3.1 Experimental processes of nanomaterial-cellulose membranes fabrication 28 2.3.2 Investigation on photocatalytic performance of nanomaterial-cellulose membranes 31 2.4 Measurements and analysis methods 34 v 2.4.1 Measurements and analysis methods of fabricated materials 34 2.4.2 Photocatalytic measurement in continuous reactor (PMRs) 36 RESULTS AND DISCUSSION 38 3.1 Survey for optimal conditions and fabricated materials 38 3.2 Characterization and properties of fabricated materials 41 3.3 Photocatalytic performance of obtained materials 48 3.3.1 Photocatalytic performance in batch reactor 48 3.3.2 Photocatalytic performance in continuous reactor (PMRs) 50 CONCLUSION 54 REFERENCES 55 APPENDIX 1: THE RESULTS OF EXPERIMENT 61 APPENDIX 2: EXPERIMENTAL IMAGES 65 vi List of Figures Figure 1.1 Textile wastewater pollution at La Khe Panel, Duong Noi, Ha Dong Figure 1.2 Textille and dyeing wastewater of craft villages Phuong La (Hung Ha, Thai Binh) is discharged into the environment Figure 1.3 (A, B, C, D) Suitable treatments for color removal a: bias = polarization of the titanium dioxide network b: CAT = catalyst c: WAO= Wet Air Oxidation d: CWAO = Catalytic Wet Air Oxidation [3] Figure 1.4 Classification of pressure-driven membrane filtration, and their pore size and pressure relationship 15 Figure 1.5 Crystal structure of titanium dioxide phases of rutile, brookite and anatase [46] 17 Figure 1.6 Mechanism of photocatalytic reaction [48] 18 Figure 1.7 Comparison between TiO2 and Au/TiO2 reaction 20 Figure 1.8 Cellulose structure 21 Figure 2.1 Experimental procedures of the research 28 Figure 2.2 Steps of CellP and CellCN synthesis 30 Figure 2.3 Procedure of CellP and CellCN fabrication 30 Figure 2.4 Photocatalytic performmance in batch reator 31 Figure 2.5 Schematic diagram of lab scale PMR system 32 Figure 2.6 PMR system in laboratory 33 Figure 2.7 PMR cell 33 Figure 2.8 UV Cell 34 Figure 2.9 Home-made filtration system 35 Figure 2.10 Apparatus to measure PEG concentration after going through nanomaterial-cellulose membranes 35 Figure 3.1 NP-cellulose membranes of TiO2 and CN with co-solvent 39 Figure 3.2 CellP with various ratios of DMSO:TBPH (ml:ml) 0.1:1 (A); 0.2:1 (B); 0.35:1 (C); 0.6:1 (D); 1.1:1 (E), respectively 39 Figure 3.3 CellCN with various ratios of DMSO:TBPH (ml:ml) 0.1:1 (A); 0.2:1 (B); 0.35:1 (C); 0.6:1 (D); 1.1:1 (E), respectively 39 Figure 3.4 (A) Adding a suspension of Au/TiO2 with 0.1 ml DMSO to cellulose solution; (B) Adding cellulose solution into a suspension of Au/TiO with 0.1 ml DMSO; (C) Adding Au/TiO2 powder into cellulose sollution; (a) CellP5, (b) CellP10, (c) CellP15, (d) CellP30, respectively 40 Figure 3.5 CellP and CellCN with different weight ratios of photocatalysts and Cell 41 Figure 3.6 (A) FT-IR spectra; (B) UV-VIS spectra of Cell; and (C) XRD spectra, Au/P25, Au/CN, CellP30 and CellCN30 The spectra are labelled as a-Cell, bvii Au/P25, c-CellP30, d-Au/CN, e)-CellCN30; (D)TEM –HAADF spectra of CellP30 43 Figure 3.7 Pore size of A) CellP and B) CellCN 45 Figure 3.8 Water Flux of (A) Cell and CellP; 47 Figure 3.9 Photocatalytic performance of cellulose-photocatalyst composite films in batch MB photodegradation 49 Figure 3.10 Continuous flow UV-Vis spectroscopy for methylene blue after going through CellP30 and CellCN30 under UV-Vis and Visible irradiation (a) Absorbance over the time, (b) Efficiency over the time 51 Figure 3.11 Continuous flow UV-Vis spectroscopy for methylene blue (a) CellP30, (b) CellCN30, without irradiation and with UV-Vis irradiation 52 viii List of Tables Table 1.1 Water comsumption of textile wastewater Table 1.2 Components of textile wastewater Table 3.1 Gold content of the photocatalyst-cellulose composite membranes 42 Table 3.2 Permeability of cellulose-photocatalyst composite membranes 46 Table 3.3 Charge dyes-dependent absorbance of CellP30 and CelllCN30 after 30 minutes reaction without irradiation 50 ix Figure 3.11 Continuous flow UV-Vis spectroscopy for methylene blue (a) CellP30, (b) CellCN30, without irradiation and with UV-Vis irradiation 52 The effect of irradiation on MB degradation by CellCN30 was displayed on Figure 3.11-b At the beginning, the absorbance of after-membrane solution increased significantly to 1.6 a.u after nearly 17 hours This can be explained by the strong absorbance of cellulose membrane with a positive charge dye as methylene blue After turning on the UV light, the absorbance went down suddenly to less than 0.5 a.u within roughly next hours It is probable that the trend would be stable from the 22th hour onwards The same tendency happened to CellP30 This result confirmed that a large proportion of decomposition stems from photocatalysis 53 CONCLUSION The manufacturing of the nanomaterial-cellulose membranes was enabled by blending Au/TiO2 or Au/sg-C3N4 into the cellulose solution at 23°C Then, the suspension was casted with the thickness of 500 µm before a coagulation with PC to obtain homogeneous films Composite membranes of different ratios of the nanomaterial (5 wt.%, 10 wt.%, 15 wt.%, 30 wt.%) of Au/TiO2 and Au/sg-C3N4, named as CellP and CellCN, respectively, followed by the amount of catalyst, stable in water and can be stored for several months Au NPs can be inserted onto the cellulose film nearly without loss, up to 99% Insertion of the photocatalysts did not change the cellulose structure, agglomeration of titanium oxide and cellulose as well as homogeneously distributed Au particles of size between and 15 nm were observed The space between the microfibrils was not changed by Au/TiO2 while Au/sg-C3N4 results in an increase in the distance There is an insignificantly morphological conversion induced by catalyst particles Photocatalytic performance via MB degradation was investigated in both batch reactor and PMRs under UV-Vis, Vis and without irradiation In batch process, 45.7% and 38.5% of degradation come from CellP30 and CellCN30, respectively, originated from absorbance capacity of composites The presence of cellulose has almost no effect on photodegradation of photocatalysts CellCN30 exhibit a better photodegradation in comparison to CellP30, especially under visible irradiation with 78.6% compared to 66.6%, respectively The photocatalytic performance also depends on charge interaction between cellulose membranes and tested dyes Positive charge dyes tend to absorb membranes better than negative or neutral charge dyes These are in favor of the possibility that a significant proportion of decomposition stems from photocatalysis The materials made of cellulose as abundant, renewable, environmentally friendly resource, offered more cost-effective and sustainable technologies for water treatment Future work: Develop modified films with better durable goods and stability Assess the capacity of obtained materials with various dyes such as negative or neutral charge dyes in PMR system to confirm the proportion of decomposition stems from photocatalysis 54 10 11 12 13 14 REFERENCES Mashkoor, F., A Nasar, and A.M.J.S.r Asiri, Exploring the reusability of synthetically contaminated wastewater containing crystal violet dye using tectona grandis sawdust as a very low-cost 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and adsorption methods 2018 2(2): p 1-3 78 79 80 81 Ngo, A.B., H.L Nguyen, and D Hollmann, Criticial Assessment of the Photocatalytic Reduction of Cr(VI) over Au/TiO2 Catalysts, 2018 8(12): p 606 Priebe, J.B., et al., Solar Hydrogen Production by Plasmonic Au–TiO2 Catalysts: Impact of Synthesis Protocol and TiO2 Phase on Charge Transfer Efficiency and H2 Evolution Rates ACS Catalysis, 2015 5(4): p 2137-2148 Priebe, J.B., et al., Water reduction with visible light: synergy between optical transitions and electron transfer in Au-TiO(2) catalysts visualized by in situ EPR spectroscopy Angew Chem Int Ed., 2013 52(43): p 11420-4 60 APPENDIX 1: THE RESULTS OF EXPERIMENT Table App 1.1 Poresize measurement using molecular weight cut-off PEG 8000 Concentration Concentration % of start HPLC of end % Mem Time Went solution results solution Retention through (ppm) (ppm) 1931.7 CellP 1924.0 1926.3 96.2 3.8 1923.3 2003.8 CellP5 2010.1 2010.5 100.4 -0.4 2017.8 1846.2 CellP10 2000 1856.7 1857.7 92.8 7.2 1870.4 2005.1 CellP15 2009.1 2002.4 100.0 0.0 1993.0 2013.6 CellP30 2010.5 2011.5 100.5 -0.5 2010.5 61 Table App 1.2 Poresize measurement using molecular weight cut-off PEG 35000 Concentration Concentration % of start HPLC of end % Mem Time Went solution results solution Retention through (ppm) (ppm) 1826.8 CellP 1832.4 1834.8 91.8 8.2 1845.2 1329.6 CellP5 1349.8 1341.5 67.1 32.9 1345.1 1716.4 CellP10 2000 1709.1 1711.2 85.6 14.4 1708.0 1991.7 CellP15 1992.6 1995.0 99.8 0.2 2000.5 1838.2 CellP30 1813.5 1827.3 91.4 8.6 1830.3 62 Table App 1.3 Poresize measurement using molecular weight cut-off PEO 200000 Concentration Concentration % of start HPLC of end % Mem Time Went solution results solution Retention through (ppm) (ppm) 1392.2 CellP 1411.8 1405.4 69.8 30.2 1412.1 1702.6 CellP5 1675.9 1695.8 84.2 15.8 1708.9 1597.9 CellP10 2000 1456.4 1548.7 76.9 23.1 1591.8 1607.2 CellP15 1588.9 1597.8 79.9 20.1 1597.4 1577.0 CellP30 1611.6 1571.8 78.1 21.9 1526.7 63 Table App 1.4 Poresize measurement using molecular weight cut-off PEO 400000 Concentration Concentration % of start HPLC of end % Mem Time Went solution results solution Retention through (ppm) (ppm) 141.9 CellP 139.6 142.0 7.1 92.9 144.4 136.9 CellP5 129.2 133.9 6.7 93.3 135.5 125.6 CellP10 2000 133.8 129.4 6.4 93.6 128.7 148.1 CellP15 149.2 148.7 7.4 92.6 148.9 133.7 CellP30 134.0 6.7 93.3 134.2 Table App 1.5 Identify error by repeating patterns Mem Concentration of start solution (ppm) Time 2000 3 CellP CellP5 CellP10 HPLC results 1565.8 1566.2 1599.2 1615.5 1605.1 1614.3 1534.2 1509.2 1536.7 Error: 21 ± 2.1 (10%) 64 Concentration % of end % Went solution Retention through (ppm) 1577.0 78.9 21.1 1611.6 80.6 19.4 1526.7 76.3 23.7 APPENDIX 2: EXPERIMENTAL IMAGES Casting machine Suspension of cellulose and sg-CN after casting Membrane coagulation in PC Cellulose solution 65 HPLC system Batch reator PMR reactor 66 ... capacity, and photodegradation under light irradiations Thus, the topic: ? ?Innovative procedure for incorporating nanomaterial onto cellulose membranes and its application in color removal from water? ??... 13 1.3 Color removal from water by nanomaterial- cellulose membranes 14 1.3.1 Basis for methods of color removal in water 14 1.3.2 Mechanism for color treatment in water 16... substances In such cases, both true color and apparent color should be assessed The color of water is determined by the standard color range in Pt-Co units The color in water depends on insoluble