本研究通過開發非對稱電容去離子（CDI）系統展示了一種綜合水處理方法。 農業廢棄玉米芯被用作生物炭合成的原料，有助於減少廢物的產生。 此外，這項研究還選擇了低成本的鎳鈷礦（NiCo2O4），一種天然豐富的尖晶石氧化物充當具有高電吸附和能量回收潛力的材料的前驅物。接著， 採用一步法活化生物炭合成結合濃硝酸（HNO3）功能修飾技術，生產出高比表面積（1，020 m2 / g）和高比電容（200.3 F / g）的生物炭（fB）。然後，該生物炭被用作NiCo2O4（NCO@fB）納米花的導電支架，通過簡單的水熱合成出具有豐富電活性位點的複合材料。 隨後，將生物炭和NCO@fB組裝在一起，分別用作不對稱CDI裝置的陽極和陰極。 最后，該系統的脫鹽性能檢查是以固定的進料溶液濃度（20 mM NaCl），但不同的施加電壓（1.0, 1.2 和1.4 V）和進料流速（10和15 mL / min），在間歇模式下進行。 此1.4 V – 10 mL/min CDI裝置能夠以74.44 ± 14.05 mg / g比電吸附電容（SEC）和18.35 ± 2.07 mg / g比電吸附率（SER）實現高脫鹽和高速率性能。 此外，這項工作也可視為開發尖晶石型金屬用於苦鹹水淡化，oxide@biochar複合材料的基礎研究。 此 CDI 設置的相應充電效率 (CE) 和比能耗 (E) 分別為 127.9 ± 7.63% 和 0.40 ± 0.05 kWh/kg 的鹽。

關鍵詞： 非對稱電容去離子（CDI），功能化生物炭，生物炭支架，尖晶石氧化物，鎳鈷礦（NiCo2O4），尖晶石氧化物-生物炭複合材料

This study demonstrates an integrated approach for water treatment by developing an asymmetric capacitive deionization (CDI) system. Agricultural waste corncob was used as raw material for biochar synthesis to help ease waste generation. Also, low-cost nickel cobaltite (NiCo2O4), a spinel oxide from naturally abundant precursors, was chosen to represent materials with high potential for electrosorption processes and energy recovery. One-step activated biochar synthesis coupled with concentrated nitric acid (HNO3) functionalization was employed to generate high surface area (1,020 m2/g) and high specific capacitance (200.3 F/g) biochar (fB). This biochar was then used as the conductive scaffold for NiCo2O4 (NCO@fB) nanoflowers with rich electroactive sites via simple hydrothermal synthesis. The asymmetric CDI setup was assembled with the biochar and NCO@fB acting as anode and cathode respectively. This system was examined with a feed of 20 mM NaCl solution under varied applied voltages (1.0 V, 1,2 and 1.4 V) and feed flowrates (10 and 15 mL/min) in batch mode. The 1.4 V – 10 mL/min CDI setup was able to achieve high desalination and high-rate performance with 74.44 ± 14.05 mg/g specific electrosorption capacitance (SEC) and 18.35 ± 2.07 mg/g specific electrosorption rate (SER). The corresponding charge efficiency (CE) and specific energy consumption (E) at this CDI setup are 127.9 ± 7.63% and 0.40 ± 0.05 kWh/kg of salt respectively. Furthermore, this work serves as a foundational study for developing spinel type metal – oxide@biochar composites for brackish water desalination.

Keywords: Asymmetric capacitive deionization (CDI), functionalized biochar, biochar scaffold, spinel oxide, nickel cobaltite (NiCo2O4), spinel – oxide@biochar composite

中文摘要 II
ABSTRACT III
ACKNOWLEDGMENT IV
TABLE OF CONTENTS V
LIST OF TABLES IX
LIST OF FIGURES XI
LIST OF APPENDICES XVI
LIST OF APPENDIX TABLES XVII
LIST OF APPENDIX FIGURES XVIII
1. INTRODUCTION 1
1.1 Background and Significance of the Study 1
1.1.1 Diversifying solutions to water crisis 2
1.1.2 Influencing technological standpoint 3
1.2 Motivation of the Study 4
1.3 Objectives and Scope 7
2. REVIEW OF LITERATURE 9
2.1. Integrative Approaches on Solving the Water Crisis 9
2.1.1 Refining terminologies for navigating water-related situations 9
2.1.2 Sustainability and nexus thinking 11
2.1.3 Treatment technologies and prospects 13
2.2. Capacitive Deionization 15
2.2.1 Basic principles 15
2.2.2 Electrode materials and ion storage mechanisms 17
2.2.3 System architectures: modifications on configurations 19
Membrane CDI (mCDI) 22
Flow CDI (fCDI) 24
Hybrid CDI (hCDI) 25
Faradaic Electrochemical Desalination (FDI) systems 26
Rocking chair CDI (RCDI). 27
Desalination batteries 29
2.2.4 Outlook for CDI 31
Developmental trends 31
Comparisons and hybrids with other technologies. 32
2.2.5 Performance determinants 39
Material characteristics 41
Material performance indicators 43
Cell characteristics 46
Operating conditions 47
2.2.6 CDI performance metrics 50
2.3. Biochar as Electrosorption Material for Capacitive Deionization 53
2.3.1 Biochar – a value-added product from biomass valorization 53
2.3.2 Performance in capacitive deionization 55
Important material properties 56
Influence of material choice, synthesis and activation 57
Existing biochar utilization in CDI 60
2.4. Nickel Cobaltite at Early Stages of Capacitive Deionization Studies 63
2.4.1 Nickel cobaltite properties and synthesis 63
2.4.2 Spinel metal oxides for capacitive deionization 64
2.5. Corncob Biochar – Nickel Cobaltite Composite for Capacitive Deionization 66
2.5.2 Corncob as feedstock for biochar synthesis 67
2.5.3 Nickel cobaltite anchored on conductive supports 69
2.5.4 NCO@biochar composite for capacitive deionization 70
3. MATERIALS AND METHODS 71
3.1. Reagents 71
3.2. Experimental Flowchart 71
3.3. Biochar 72
3.3.1 Biochar design parameters 72
3.3.2 Biochar synthesis 73
One-step synthesis of activated biochar 73
Functionalization of activated biochar 74
3.4. Nickel Cobaltite on Functionalized Biochar 75
3.5. Material Characterization 76
3.6. Electrochemical Performance Tests 77
3.6.1. Material preparation 77
3.6.2. Cyclic voltammetry and electrochemical impedance spectroscopy 77
3.7. Capacitive Deionization 78
3.7.1. Experimental 78
3.7.2. Parametric study 80
3.7.3. Performance matrix 81
4. RESULTS AND DISCUSSION 83
4.1. Biochar Design 84
4.1.1. General observations on surface and structure 84
4.1.2. Individual and interaction of parameter effects on biochar characteristics 89
4.1.3. Functionality 93
4.1.4. Electrochemical performance 95
Effect of surface and structural characteristics of biochar 99
Effect of functionalization 100
4.1.5. Summary of biochar design 102
4.2. NCO@fB nanocomposite 103
4.2.1. Characterization 103
4.2.2. Electrochemical performance 110
4.3. Capacitive deionization performance 116
4.3.1. Desalination capacity and kinetics 116
4.3.2. Effect of parameters on material performance 120
4.3.3. Energy performance 122
4.3.4. Desalination mechanism 128
5. SUMMARY AND CONCLUSION 131
6. REFERENCES 133
APPENDICES 150
APPENDIX A 150
APPENDIX B 154
APPENDIX C 155
APPENDIX D 157
APPENDIX E 159
APPENDIX F 160

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