Nghiên cứu vật liệu nano siêu mỏng mos2 pha tạp nitơ và vật liệu tổng hợp graphene mos2 chế tạo bằng phương pháp điện hóa plasma ứng dụng cho phản ứng sản sinh hydrô

國國國國國國 國國國國國國國國國 國國國國 國國國國國國國國國國國國國國國國國國國國國國-國國 國國國國國國國國國國國國 Nitrogen Doped MoS2 Nanosheets and Graphene/MoS2 Composite Prepared by Electrolysis Plasma-Induced Process for Hydrogen Evolution Reaction 國國國: 國國國 國國國國國國國國 國 國 國國國國國國國國國國 國國國國國國國國國國國國國國國國國國國國國國-國國國國國國 國國國國國國國國 Nitrogen Doped MoS2 Nanosheets and Graphene/MoS2 Composite Prepared by Electrolysis Plasma-Induced Process for Hydrogen Evolution Reaction 國國國國國國國 Student: Nguyen Van Truong 國國國國國國國國 國國 Advisor: Dr Kung-Hwa Wei 國國國國國國 國國國國國國國國國 國國國國 A Dissertation Submitted to Department of Materials Science and Engineering College of Engineering National Chiao Tung University in partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Materials Science and Engineering March 2020 Hsinchu, Taiwan, Republic of China 國國國國國國國國國國 國國 國國國國國國國國國國國國國國國國國國國國國國國國國國國HER國國國國國國國國國 國國國國國國國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國 國國國國國/ 國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國 國國國國國國國 80°C國國國國國國國國國國國國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國 國 2H-國國國國 國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國 –2 國國國國國國國國國國國國國國國 5.2 at國國國 國國國國國國國國國國國國國國 10 mA cm 國國國國國國國國國國國國 164 -1 -1 mV國Tafel 國國國國國國 71 mV dec –國國國國國國國國國國國國國國207 mV國82 mV dec 國國國 國國國國 -1 國國602 mV國198 mV dec 國國國國國 0.5 M 國國國國國 25 國國國國國國國國 國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國國國OGNs @ 國國國國國國國國國國國國國國國 國國國國國國國國GNs @ 國國國國國國國國國國國國國國國國國國國國國國 HER 國國 國國國國國國國國國國國國國國國國國國國-國 國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國國 HER 國國國國國國國國國國國國國國國 OGNs -2 @ 國國國國國國國國國國國國國國 HER 國國國國 10 mA cm 國國國國國國國國 118 mV 國國國國國國Tafel 國國 國 dec-1 國 Tafel 國國國國國國國國國國國國國國國國國國國國 國國國國國國國國國國國國國國國國國 GNs @ 國國國國 -1 國182 mV國82 mV dec 國國國國 國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國國 國TMDCs國國國國國國國國國國國國國 TMDCs 國國國國國國國國國國國國國國國國國 國國國國 i Nitrogen Doped MoS2 Nanosheets and Graphene/MoS2 Composite Prepared by Electrolysis Plasma-Induced Process for Hydrogen Evolution Reaction Student: Nguyen Van Truong Advisor: Prof Kung-Hwa Wei Department of Materials Science and Engineering National Chiao Tung University Abstract With the goal of obtaining sustainable earth-abundant electrocatalyst materials displaying high performance in the hydrogen evolution reaction (HER), here we propose a facile one-pot plasma-induced electrochemical process for the fabrication of both nitrogen-doped MoS2 nanosheets and graphene/MoS2 composite An efficient one-step approach that involves simultaneous plasma-induced doping and exfoliating of MoS2 nanosheets within a short time and at a low temperature (ca 80 °C) has been developed Particularly, an active plasma zone can be generated at the submerged cathode tip to achieve doping of nitrogen atoms into the semiconducting 2H-MoS2 structure The electronic and transport properties were modulated under the synergy of the nitrogen doping and exfoliation in the MoS2 structure to enhance their catalytic activation It is found that the N concentration of 5.2 at % at N-doped MoS2 nanosheets have excellent catalytic hydrogen evolution reaction where a low over-potential of 164 mV at a current density of 10 mA cm–2 and a small Tafel slope of 71 mV dec–1—much –1 lower than those of exfoliated MoS2 nanosheets (207 mV, 82 mV dec ) and bulk MoS2 (602 mV, 198 mV dec–1)—as well as an extraordinary long-term stability of >25 h in 0.5 M H2SO4 can be achieved Interestingly, through a simple selection of cathode materials in one-batch process, two different morphologies of graphene sheets were obtained, resulting in both onion-like covered MoS2 nanosheets (OGNs@MoS2) and sheets-like graphene wrapped MoS2 composites (GNs@MoS2) We found that the presence of the graphene sheets appeared to be ii a key aspect of the enhanced HER ability Therefore, we conclude that electronic coupling at the graphene– ii MoS2 nanosheet interfaces also played an important role in enhancing the HER activity Our OGNs@MoS2 composites exhibited high HER performance, characterized by a low overpotential of 118 mV at a current density of 10 mA cm–2, a Tafel slope of 73 mV dec–1, and long-time stability without degradation; this performance is much better than that of the sheetlike graphene-wrapped MoS2 composite GNs@MoS2 (182 mV, 82 mV dec–1) This approach appears to be an effective and simple strategy for tuning not only nitrogen-doped transition metal dichalcogenide (TMDCs) materials but also the morphologies of composites of graphene and TMDCs materials for a broad range of energy applications KEYWORDS: MoS2, Nitrogen doped MoS2, Onion-like graphene, Graphene/MoS2 composite, One-pot Plasma-Induced exfoliation, Hydrogen evolution reaction, electrocatalyst ACKNOWLEDGMENTS This dissertation presents a summary of my research work which has done in the Department of Materials Science and Engineering (MSE), National Chiao Tung University (NCTU) It is a pleasure to express my sincere gratitude to all the people who helped and supported me during my Ph.D study From bottom of my heart I express my deep sense of gratitude and profound respect to my supervisor Prof Kung-Hwa Wei He continually and convincingly conveyed a spirit of adventure in regard to research and scholarship, and an excitement in regard to teaching Without his generous encouragement and brief advice for those years, this dissertation would not have been completed My sincere thanks Prof Yu-Lun Chueh for his kind guidance and persistent help I would like to thank Dr Yen Po-Jen, Dr Cheng Hao-Wen, Dr Chen Hsiu-Cheng, Dr VanQui Le, Mr Phuoc Anh Le, Mr Chung-Hao Chen, Mr Tzu-Yi Yang, Mr Yung-Chi Hsu, Mr Bo-Hsien Lin for their kind supporting in my research Many thanks to all participants in Prof Kung-Hwa Wei’s lab who took part in the study and enabled this dissertation to be possible In addition, I would like to thank all members of Vietnamese Student Association-NCTU who made my life in Taiwan really pleasurable and joyful Finally, special thanks for my parent, my wife and my two angels who always standing by my side Thank you for always encouraging me to pursue my dreams I love you all so much, thanks for loving me too! Nguyen Van Truong Hsinchu, Taiwan April 2020 Table of Content 國 國 .i Abstract .ii Acknowledgment .iv Table of Content v Figures list .vii Tables list xi Chapter Introduction 1.1 Introduction of Transition metal dichalcogenides 1.2 Production of Transition Metal Dichalcogenides materials 1.3 Introduction of cathodic plasma exfoliation method 1.4 Introduction of Electrocatalytic Hydrogen Evolution Reaction 1.5 Introduction of nitrogen doped MoS2 .12 1.6 Introduction of graphene/MoS2 composite .14 1.7 Strategies to enhancing MoS2 catalytic activity .16 1.8 Thesis outline 20 Chapter Production Nitrogen-Doped Molybdenum Disulfide nanosheets through Plasma-Induced process and their electrocatalyst performance 21 2.1 Introduction 21 2.2 Experimental section 24 2.3 Results and discussion 27 2.4 Conclusions 50 Chapter Production Graphene/MoS2 composite through One-Pot Plasma-Induced process and their Electrocatalyst performance 51 3.1 Introduction 51 3.2 Experimental section 54 3.3 Results and discussion 58 3.4 Conclusions 83 Chapter Conclusions 84 References 87 Vita 99 Publications list 101 Figures list Figure 1.1 The periodic table with highlighted transition metal and chalcogenide elements that form layered TMDCs materials .1 Figure 1.2 The crystal struture of TMDCs with Octahedral (1T), Trigonal prismatic (2H) and (3R) coordination Figure 1.3 Six main production methods of TMDCs and their content Figure 1.4 Several TMDCs nanosheets production methods Figure 1.5 Typical of plasma electrolysis and its applications Figure 1.6 Experimental setup and mechanism of cathodic plasma exfoliation Figure 1.7 Schematic representation of the proposed mechanism of plasma exfoliation and nitrogen-doping Figure 1.8 I-V curve of overall water splitting 10 Figure 1.9 Schematic of the covalent nitrogen doping in MoS2 upon N2 plasma surface treatment 13 Figure 1.10 (a) Schematic illustration of the electrochemical deposition set-up; 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(b) Schematic representation of the proposed mechanism of OGNs @MoS2 and GNs @MoS2 58