Green synthesis of carbon doped zinc oxide using garcinia mangostana pericarp extract for photocatalytic degradation of methylene blue and photoproduction of hydrogen peroxide applications

VIETNAM NATIONAL UNIVERSITY HO CHI MINH CITY HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY LE MINH HUONG GREEN SYNTHESIS OF CARBON-DOPED ZINC OXIDE USING GARCINIA MANGOSTANA PERICARP EXTRACT FOR PHOTOCATALYTIC DEGRADATION OF METHYLENE BLUE AND PHOTOPRODUCTION OF HYDROGEN PEROXIDE APPLICATIONS Major: Chemical Engineering Major code: 8.52.03.01 MASTER’S THESIS HO CHI MINH CITY, July 2023 THIS THESIS IS COMPLETED AT HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY – VNU-HCM Supervisor: Assoc Prof Nguyen Huu Hieu, Ph.D Vo Nguyen Dai Viet, Ph.D Examiner 1: Assoc Prof Tran Ngoc Quyen, Ph.D Examiner 2: Assoc Prof Nguyen Tuan Anh, Ph.D This master’s thesis is defended at HCM City University of Technology – VNU- HCM City on July 24, 2023 Master’s Thesis Committee: Assoc Prof Nguyen Truong Son, Ph.D – Chairman of the thesis committee; Assoc Prof Tran Ngoc Quyen, Ph.D – Reviewer 1; Assoc Prof Nguyen Tuan Anh, Ph.D – Reviewer 2; Ly Tan Nhiem, Ph.D – Spokesperson; Pham Trong Liem Chau, Ph.D – Scientific secretary Approval of the Chairman of Master’s Thesis Committee and Dean of Faculty of Chemical Engineering after the thesis being corrected (If any) CHAIRMAN OF HEAD OF FACULTY OF THESIS COMMITTEE CHEMICAL ENGINEERING (Signature with full name) (Signature with full name) i Ho Chi Minh City University of Technology – VNU-HCM Faculty of Chemical Engineering SOCIALIST REPUBLIC OF VIETNAM Independence – Freedom – Happiness THESIS TASK ASSIGNMENT Student’s name: Le Minh Huong ID: 2270006 Date of birth: 07/11/1999 Place of birth: Ho Chi Minh city Major: Chemical Engineering Code: 8.52.03.01 Title: Title in Vietnamese: Tổng hợp xanh vật liệu kẽm oxit pha tạp cacbon từ dịch chiết vỏ măng cụt ứng dụng để quang phân hủy xanh methylene quang tổng hợp hydroperoxide Title in English: Green synthesis of carbon-doped zinc oxide using Garcinia mangostana pericarp extract for photocatalytic degradation of methylene blue and photoproduction of hydrogen peroxide applications Assignment: 2.1 Literature review Dye pollution, methylene blue (MB), energy crisis, hydrogen peroxide (H2O2), zinc oxide (ZnO), synthesis routes of ZnO, photocatalysis, carbon-doped zinc oxide (ZnO-C), photocatalytic mechanism, green synthesis, Garcinia mangostana pericarp extract 2.2 Experimental - Preparation of Garcinia mangostana pericarp extract; - Influences of calcination conditions on the characteristics and MB photodegradation performance of ZnO-C prepared from Garcinia mangostana pericarp extract calcinated at various temperatures and times; - Characterization of the suitable ZnO-C; - Photodegradation of MB using ZnO-C, the related photocatalysis mechanism, reusability, and recyclability of ZnO-C for the removal of MB; - Photoproduction of H2O2 in the presence of ZnO-C, the corresponding photocatalysis mechanism, reusability, and recyclability of ZnO-C for the production of H2O2 Assignment date: 02/2023 Completion date: 07/2023 Supervisor: Assoc Prof Nguyen Huu Hieu, Ph.D.; Vo Nguyen Dai Viet, Ph.D Ho Chi Minh City, July 12, 2023 SUPERVISOR HEAD OF KEY LABORATORY (Signature with full name) (Signature with full name) NGUYEN HUU HIEU VO NGUYEN DAI VIET NGUYEN HUU HIEU HEAD OF FACULTY OF CHEMICAL ENGINEERING (Signature with full name) ii ACKNOWLEDGEMENTS Ever since I was born, my parents, especially my mom, have cherished me and cheered me for every step that I took in my life Little by little, I always tried my best to achieve the goals that I have set Four years of studying as well as two years of researching has brought me tons of experience along with memorable moments at Ho Chi Minh City University of Technology (HCMUT) – Vietnam National University Ho Chi Minh City (VNU-HCM) Every time I met a dead end during my enrollment and research in this university, it has and always been my mom who gave me the courage and the strength to continue to pursue my dreams and goals I would like to send my special thanks of gratitude to Assoc Prof Nguyen Huu Hieu, Ph.D and Vo Nguyen Dai Viet, Ph.D I have learned various skills and knowledge from them not only just academic knowledge but also their ways of thinking and problem-solving Their thoroughness has helped a lot during research Without Their dedication, my thesis would not be implemented in time I would also like to send my appreciation to all the members of VNU-HCM, Key Laboratory of Chemical Engineering and Petroleum Processing (Key CEPP Lab), HCMUT – VNU-HCM I hope that one day I can return to this university to recall all the memorable moments that I have had during years of enrollment Ho Chi Minh City, July 2023 Author Le Minh Huong iii ABSTRACT In this study, carbon doped-zinc oxide (ZnO-C) was green synthesized using Garcinia mangostana pericarp extract and calcination The influences of calcination temperature and time on the characteristics and methylene blue (MB) photodegradation performance of ZnO-C The samples calcinated at various temperatures and times were characterized with scanning electron microscopy, thermal gravimetry analysis-differential thermal analysis, energy-dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffraction The ZnO-C sample calcinated at favorable temperature and time was characterized via transmission electron microscopy, Raman spectroscopy, nitrogen adsorptiondesorption isotherms, ultraviolet–visible diffuse reflectance spectroscopy, electrochemical impedance spectroscopy, cyclic voltammetry, and photoluminescence spectroscopy Simultaneously, the band structure of ZnO-C was also calculated The photodegradation of MB using ZnO-C was assessed The individual influences of factors such as catalyst doses (40, 50, and 60 mg), pH (3, 5, 7, 9, and 11), and initial dye concentrations (5, 10, 15, 20, and 25 mg/L) were evaluated The photocatalysis mechanism of ZnO-C for MB was proposed via total organic carbon and chemical oxygen demand and radical scavenger results The reusability and recyclability of ZnOC for this process were studied after 10 cycles were also evaluated The photoproduction of H2O2 was also studied the impacts of electron donors (methanol and isopropanol), its volumes (2.5, 5.0, and 7.5 mL), and catalyst doses (2.5, 5.0, and 7.5 mg) on the photoproduction of hydrogen peroxide using ZnO-C prepared at favorable conditions was individually studied The mechanism of ZnO-C for the photoproduction of hydrogen peroxide was suggested based on the determined band structure of ZnO and redox potentials of radicals and hydrogen peroxide The reusability and recyclability of ZnO-C for this process were similarly studied after 10 cycles The works done in this thesis are summarized in Figure iv Figure Work done in this thesis v TÓM TẮT Trong nghiên cứu này, kẽm oxit pha tạp cacbon (ZnO-C) tổng hợp xanh từ dịch chiết vỏ măng cụt Ảnh hưởng nhiệt độ nung thời gian nung đến đặc trưng hiệu suất xúc tác quang phân hủy xanh methylene (MB) ZnO-C khảo sát Đặc trưng vật liệu ZnO-C nung nhiệt độ thời gian khác khảo sát phương pháp phân tích như: Kính hiển vi điện tử quét, phổ tán xạ lượng tia X, phân tích nhiệt trọng lượng-nhiệt vi sai, quang phổ hồng ngoại biến đổi Fourier, nhiễu xạ tia X Đặc trưng vật liệu ZnO-C nung nhiệt độ thời gian phù hợp khảo sát kính hiển vi điện tử truyền qua, phổ Raman, đường đẳng nhiệt hấp phụ-giải hấp nitơ, quang phổ phản xạ khuếch tán tử ngoại khả kiến, phổ trở kháng điện hóa, vơn kế tuần hồn,và quang phổ huỳnh quang Đồng thời, lượng vùng dẫn vùng hóa trị vật liệu ZnO-C xác định Hiệu suất quang phân hủy ZnO-C xanh metylene (MB) khảo sát Ảnh hưởng lượng chất xúc tác (40, 50, 60 mg), pH (3, 5, 7, 9, 11), nồng độ MB (5, 10, 15, 20, 25 mg/L) lên hiệu suất quang phân hủy MB khảo sát Cơ chế quang phân hủy xanh metylen vật liệu ZnO-C đề xuất thông qua tổng lượng carbon hữu cơ, nhu cầu oxy hóa học, ảnh hưởng chất tự đến hiệu suất quang phân hủy MB Khả thu hồi tái sử dụng vật liệu ZnO-C khảo sát qua 10 chu kỳ tái sử dụng liên tiếp để đánh giả khả tái sử dụng vật liệu ZnO-C Quá trình quang tổng hợp hydroperoxide (H2O2) sử dụng vật liệu ZnO-C khảo sát Ảnh hưởng chất cho điện tử (methanol isopropanol), thể tích chất cho điện tử (2,5, 5,0, 7,5 mL), lượng xúc tác (2,5, 5,0, 7,5 mg) vật liệu ZnO-C trình quang tổng hợp H2O2 khảo sát để tìm điều kiện phù hợp Thêm đó, chế xúc tác quang ZnO-C trình quang tổng hợp hydroperoxide đề xuất dựa lượng vùng dẫn vùng hóa trị ZnO-C Khả thu hồi tài sử dụng vật liệu ZnO-C cho trình quang tổng hợp H2O2 qua 10 chu kỳ tái sử dụng khảo sát vi COMMITMENT OF THE THESIS’ AUTHOR I hereby declare that the work is originally implemented by the author and carried out under the instructions of Assoc Prof Nguyen Huu Hieu, Ph.D and Vo Nguyen Dai Viet, Ph.D in Ho Chi Minh City University of Technology – Vietnam National University Ho Chi Minh City I confirm that this work is the result of my research and is solely my work All the contribution-related to this thesis have been fully acknowledged I affirm that any formulation, idea, research, reasoning, or analysis borrowed from a third party is correctly and accurately cited in both techniques and the author’s rights The author takes full responsibility for the full work Author Le Minh Huong vii TABLE OF CONTENTS 1.1 Dye pollution 1.1.1 Current status 1.1.2 Thiazine dye 1.1.3 Removal methods 1.2 Energy crisis 1.2.1 Current status 1.2.2 Hydrogen peroxide 1.2.3 Production methods 1.3 Zinc oxide 1.3.1 Structure 1.3.2 Properties 1.3.3 Synthesis .10 1.3.4 Photocatalyst mechanism 17 1.3.5 Applications 18 1.3.6 Modification 23 1.4 Carbon-doped zinc oxide (ZnO-C) 28 1.4.1 Structure .28 1.4.2 Photocatalyst mechanism 29 viii 1.4.3 Synthesis of ZnO-C 30 1.5 Garcinia mangostana pericarp 31 1.5.1 Current status .31 1.5.2 Extraction methods 32 1.6 Domestic and international research and status on ZnO-C 33 1.6.1 Domestic researches on ZnO-C 33 1.6.2 International researches on ZnO-C 34 1.7 Objectives, contents, methods, essentiality novelty, and contribution of thesis 35 1.7.1 Objective 35 1.7.2 Content 35 1.7.3 Research methods 36 1.7.4 Essentiality 49 1.7.5 Novelty of thesis 49 1.7.6 Contribution of thesis 50 2.1 Chemicals, materials, facilities, equipment, and work location 51 2.1.1 Chemicals and materials 51 2.1.2 Facilities 52 2.1.3 Equipment 52 2.1.4 Work location 53 2.2 Experiments 53 2.2.1 Preparation of G mangostana pericarp extract .53 2.2.2 Study on influences of calcination temperature and time on characteristics and photodegradation performance of ZnO-C toward MB 54 2.2.3 Characterization of ZnO-C calcinated at favorable temperature and time 57 2.2.4 Study on the photodegradation of methylene blue (MB), related mechanism, reusability, and recoverability of the catalyst 58 2.2.5 Study on the photoproduction of hydrogen peroxide (H2O2), corresponding mechanism, reusability, and recoverability of catalyst .61 ix Appendix Characterization of ZnO-C calcinated at favorable temperature and time Appendix Figure 2.1 SAED pattern of ZnO-C-0 Appendix Figure 2.2 SAED pattern of ZnO-C-700-1.0 158 Appendix Figure 2.3 TEM images of ZnO-C-0 159 Appendix Figure 2.4 TEM images of ZnO-C-700-1.0 160 Appendix Figure 2.5 Raman spectrum of ZnO-C-0 Appendix Figure 2.6 Raman spectrum of ZnO-C-700-1.0 161 Appendix Figure 2.7 N2 adsorption-desorption isotherms of ZnO-C-0 Appendix Figure 2.8 N2 adsorption-desorption isotherms of ZnO-C-700-1.0 162 Appendix Figure 2.9 Pore size distribution of ZnO-C-0 Appendix Figure 2.10 Pore size distribution of ZnO-C-700-1.0 163 Appendix Figure 2.11 Specific surface area of ZnO-C-0 Appendix Figure 2.12 Specific surface area of ZnO-C-700-1.0 Appendix Table 2.1 Values for the calculation of band structure of ZnO-C-700-1.0  Ionization Electron (eV) energy (eV) affinity (eV) Zn 4.70 9.39 O 7.54 13.62 1.46 C 6.26 11.26 1.59 Element 164 Appendix Photocatalytic degradation of MB Appendix 3.1 Individual influences of impacting factors Appendix 3.1.1 Influences of catalyst dose on the photodegradation of MB Appendix Table 3.1 Data for the photodegradation of MB using ZnO-C-700-1.0 with different catalyst doses Time (min) Removal efficiency (%) 50 mg 60 mg 70 mg 0 0 30 18.36  0.67 72.94  2.81 60.99  2.04 60 40.72  1.48 92.15  3.55 83.74  2.80 90 59.08  2.15 98.90  3.81 93.19  3.12 120 70.75  2.57 99.88  3.85 97.18  3.25 Appendix Table 3.2 Data for the kinetic of the photodegradation of MB using ZnO-C-700-1.0 with different catalyst doses Time (min) Ln(A/A0) 50 mg 60 mg 70 mg 0 0 30 0.20  0.07 1.31  0.05 0.94  0.03 60 0.52  0.12 2.54  0.10 1.82  0.06 90 0.89  0.13 4.51  0.17 2.69  0.09 120 1.23  0.24 6.69  0.27 3.57  0.12 165 Appendix 3.1.2 Influences of pH on the photodegradation of MB Appendix Table 3.3 Data for the photodegradation of MB using ZnO-C-700-1.0 in different pH Time (min) Removal efficiency (%) pH pH pH pH pH 11 0 0 0 30 38.26  1.32 58.47  2.25 72.94  2.93 74.75  2.39 94.96  2.84 60 62.75  2.16 84.92  3.27 92.15  3.70 98.52  3.15 99.02  2.96 90 83.31  2.87 95.71  3.69 98.90  3.97 99.83  3.19 99.92  2.98 120 90.34  3.11 99.08  3.82 99.90  4.01 99.98 3.19 99.99  2.99 Appendix Table 3.4 Data for the kinetic of the photodegradation of MB using ZnO-C-700-1.0 in different pH Time (min) Ln(A/A0) pH pH pH pH pH 11 0 0 0 30 0.48  0.02 0.88  0.03 1.31  0.05 1.38  0.04 2.99  0.09 60 0.99  0.03 1.89  0.07 2.54  0.10 4.21  0.13 4.63  0.14 90 1.79  0.06 3.15  0.12 4.51  0.18 6.35  0.20 7.13  0.21 120 2.34  0.08 4.69  0.18 6.91  0.28 8.44  0.27 9.71  0.29 166 Appendix 3.1.3 Influences of initial dye concentration on the removal of MB Appendix Table 3.5 Data for the photodegradation of MB using ZnO-C-700-1.0 with different initial dye concentrations Time (min) Removal efficiency (%) mg/L 10 mg/L 15 mg/L 20 mg/L 25 mg/L 0 0 0 30 95.69  3.29 94.96  3.66 69.23  2.78 51.31  1.64 44.21  1.32 60 99.55  3.42 99.02  3.82 91.89  3.69 73.56  2.35 62.37  1.86 90 99.95  3.44 99.92  3.85 97.23  3.90 84.98  2.71 73.32  2.19 120 99.99  3.44 99.99  3.86 99.10  3.98 92.48  2.95 85.28  2.55 Appendix Table 3.6 Data for the kinetic of photodegradation of MB using ZnO-C-700-1.0 with different initial dye concentrations Time (min) Ln(A/A0) mg/L 10 mg/L 15 mg/L 20 mg/L 25 mg/L 0 0 0 30 3.15  0.11 2.99  0.12 1.18  0.05 0.72  0.02 0.58  0.02 60 5.39  0.19 4.63  0.18 2.51  0.10 1.33  0.04 0.98  0.03 90 7.61  0.26 7.13  0.27 3.59  0.14 1.90  0.06 1.32  0.04 120 9.91  0.34 9.71  0.37 4.71  0.19 2.59  0.08 1.92  0.06 167 Appendix 3.2 Photocatalysis mechanism of ZnO for the degradation of MB Appendix 3.2.1 Data for post-catalysis analysis Appendix Table 3.7 TOC and COD removal of post-photocatalysis MB solution using ZnO-C-700 Time TOC COD (min) (%) (%) 60 75.98  2.43 67.54  2.89 120 82.75  2.58 75.67  3.23 180 89.94  2.88 80.43  3.43 240 94.76  3.03 89.98  3.73 Appendix 3.2.2 Influences of radical scavengers on the photodegradation of MB Appendix Table 3.8 Data for the photodegradation of MB using ZnO-C-700-1.0 in the presence of different radical scavengers Time (min) Removal efficiency (%) None EDTA IPA p-BQ 60 94.96  3.42 39.32  1.26 53.08  2.18 55.79  2.34 120 99.02  3.56 63.72  2.04 70.55  2.89 75.30  3.16 180 99.92  3.60 76.27  2.44 87.69  3.60 86.67  3.64 240 99.99  3.60 82.58  2.64 92.74  3.80 91.80  3.86 Appendix Table 3.9 Data for the kinetic of the photodegradation of MB using ZnO-C-700-1.0 in the presence of different radical scavengers Time (min) Ln(A/A0) None EDTA IPA p-BQ 60 2.99  0.11 0.50  0.02 0.76  0.03 0.82  0.03 120 4.63  0.17 1.01  0.03 1.22  0.05 1.40  0.06 180 7.13  0.26 1.44  0.05 2.09  0.09 2.01  0.08 240 9.71  0.35 1.75  0.06 2.62  0.11 2.50  0.11 168 Appendix 3.3 Reusability and recyclability of ZnO-C for the removal of MB Appendix Table 3.10 Data for the photodegradation of MB after 10 recovery and reuse cycles using ZnO-C-700-1.0 Cycle Removal efficiency (%) 99.99  4.20 99.32  3.38 99.01  3.86 96.98  4.12 94.78  3.97 92.23  4.04 90.14  3.95 88.56  4.08 85.72  3.32 10 82.34  3.67 Appendix Photoproduction of H2O2 Appendix 4.1 Individual influences of impacting factors Appendix 4.1.1 Influences of electron donors on the photoproduction of H2O2 Appendix table 4.1 Data for the photoproduction of H2O2 using ZnO-C-700-1.0 using different electron donors Time (min) H2O2 production (μM/g⸳h) MeOH IPA 0 30 833.86  92.60 2423.33  31.02 60 1316.43  120.13 3143.82  48.97 90 1813.96  154.71 4048.99  67.48 120 2439.37  187.48 4906.62  90.74 150 3137.44  246.47 6450.39  116.71 180 3555.85  306.03 8009.08  132.28 169 Appendix 4.1.2 Influences of volumes of donor on the photoproduction of H2O2 Appendix table 4.2 Data for the photoproduction of H2O2 using ZnO-C-700-1.0 with different volumes of IPA Time (min) H2O2 production (μM/g⸳h) 2.5 mL 5.0 mL 7.5 mL 0 0 30 1317.78  39.76 2423.33  92.60 3805.07  123.66 60 1879.52  56.71 3143.82  120.13 5449.81  177.12 90 2854.88  86.13 4048.99  154.71 7134.40  231.87 120 3779.37  114.02 4906.62  187.48 8791.93  285.74 150 4677.00  141.11 6450.39  246.47 11339.95  368.55 180 4751.79  143.36 8009.08  306.03 11585.31  368.55 Appendix 4.1.3 Influences of catalyst dose on the photoproduction of H2O2 Appendix table 4.3 Data for the photoproduction of H2O2 using different doses of ZnO-C-700-1.0 Time (min) H2O2 production (μM/g⸳h) mg 10 mg 15 mg 0 0 30 10655.07  407.13 3805.07  123.66 3594.40  137.34 60 15559.52  594.53 5449.81  177.12 4633.43  177.04 90 21607.15  825.61 7134.40  231.87 6126.96  234.11 120 29039.32  1109.59 8791.93  285.74 8324.93  318.10 150 32975.46  1259.99 11339.95  368.55 9075.07  346.76 180 38748.89  1480.60 11585.31  376.52 12286.15  469.45 170 Appendix 4.2 Reusability and recyclability of ZnO-C Appendix table 4.4 Data for the photoproduction of H2O2 after 10 recovery and reuse cycles using ZnO-C-700-1.0 Cycle H2O2 production (μM/g⸳h) 38748.89  1239.96 37954.87  1252.51 35687.98  1284.77 34655.97  762.43 32546.78  1366.96 30986.87  991.58 29999.76  875.99 28974.87  927.20 28108.46  933.20 10 27875.87  892.03 171 VITA Full name: LE MINH HUONG Date of birth: 07/11/1999 Place of birth: Ho Chi Minh City Address: 139/37 Pham Huy Thong Street, Ward, Go Vap District, Ho Chi Minh City Phone: 0334007060 Email: lmhuong0711@gmail.com EDUCATION 2017 – now: Faculty of Chemical Engineering, Ho Chi Minh City University of Technology – VNU-HCM WORK 2021 – now: VNU-HCM, Key Laboratory of Chemical Engineering and Petroleum Processing, HCMUT – VNU-HCM 172