Development of Oxydehydration Catalyst for Glycerol to Acrylic acid and Hydrogenation Catalyst of Carbon monoxide by Hetero-atom Doping Technique
이원자 도핑 기술을 이용한 아크릴산 생산용 글리세롤 산화탈수반응 촉매 및 일산화탄소 수소화 촉매 개발

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dc.description학위논문 (박사)-- 서울대학교 대학원 : 화학생물공학부, 2017. 2. 이종협.-
dc.description.abstractOver the past centuries, development of efficient catalyst for the production of fuel and fine chemicals using petroleum is one of the most important works in academic and industrial fields. As the emergence of new resources replacing fossil resources, such as biomass, shale gas, etc., new catalytic systems is highly required. Among various method to develop active catalysts, doping method have attracted attention due to its effectiveness for tuning surface properties. In this thesis, by doping hetero-atom, bi-functional catalyst for the production of value-added chemicals from biomass-derived reactant was developed, and catalytic activity was controlled by manipulating electronic properties of catalysts.
Oxydehydration of glycerol is currently attracting considerable attentions. In an attempt to develop efficient catalyst for the reaction, tungsten incorporated molybdenum vanadium mixed oxide (MoVW) catalysts were designed based on computational calculations and mechanistic insights. By incorporating tungsten into molybdenum vanadium mixed oxide (MoV) structure, the catalysts are active and selective in not only the dehydration of glycerol but also the subsequent oxidation of acrolein to acrylic acid. Structural characterization was performed by XRD, XANES, DFT calculations, Raman, and IR spectroscopies. The incorporated tungsten species enhanced the acid and redox properties of the catalyst, leading to a high selectivity to acrylic acid (30.5 %). It not only induced but also stabilized the reduced oxidation states of molybdenum and vanadium atoms, as confirmed by XPS and DFT calculations. Hence, a stable and selective production of acrylic acid was achieved with full glycerol conversion for 110 h. The MoVW catalytic system with an additional acid catalyst bed exhibited remarkable selectivity for acrylic acid (47.2 %), suggesting its potential for practical applications.
In the fundamental aspect, catalytic activity in heterogeneous catalysis was controlled by tuning electronic state of a catalyst by doping method. For controlling the electronic state of metal supported graphene catalysts, type (N and B) and concentrations of dopants was varied. The change in electronic state of active metals was confirmed by XPS analysis. Although factors affecting on activity, such as particle size, phase, loading amount, were excluded among the prepared catalysts, different catalytic activities were observed. Theoretical calculations revealed that variation in interactions between active metal and reactant, induced by tuning the electronic state, affected catalytic activity of the catalysts.
dc.description.tableofcontentsChapter 1. Introduction 1
1.1 Heterogeneous catalysis by doped catalysts 1
1.2 Design of bi-functional catalyst for glycerol oxydehydration to acrylic acid 4
1.3 Control of catalytic reactivity by tuning electronic state via doping method 5
1.4. Objectives 7

Chapter 2. Development of a bi-functional catalyst for oxydehydration of glycerol to acrylic acid 8
2.1 Introduction 8
2.2 Experimental 11
2.2.1 Preparation catalysts 11
2.2.2 Characterization 12
2.2.3 Catalytic activity test 14
2.2.4 Computational details 16
2.3 Results and discussion 18
2.3.1 Modeling of tungsten incorporated MoV catalyst by DFT 18
2.3.2 Structural characterization 20
2.3.3 Effect of incorporated tungsten on acid and redox properties 24
2.3.4 Effect of reaction temperature and contact time on activity 27
2.3.5 Effect of tungsten on catalytic activity for oxydehydration of glycerol 29
2.3.6 Effect of tungsten on catalytic stability of MoVW catalyst 32
2.3.7 Comparative activity test in two-bed system 33

Chapter 3. Control of catalytic reactivity for carbon monoxide hydrogenation by tuning electronic state via doping method 68
3.1 Introduction 68
3.2 Experimental 70
3.2.1 Preparation of catalysts 70
3.2.2 Characterization 72
3.2.3 Catalytic activity test 73
3.2.3 Computational details 74
3.3 Results and discussion 76
3.3.1 Catalyst characterization 76
3.3.2 Reaction test for CO hydrogenation 79
3.3.3 DFT calculations. 80

Chapter 4. Summary and Conclusions 91
Bibliography 94
국 문 초 록 102
dc.format.extent6590124 bytes-
dc.publisher서울대학교 대학원-
dc.subjectHeterogeneous catalyst-
dc.subjectacrylic acid-
dc.subjectelectronic state-
dc.titleDevelopment of Oxydehydration Catalyst for Glycerol to Acrylic acid and Hydrogenation Catalyst of Carbon monoxide by Hetero-atom Doping Technique-
dc.title.alternative이원자 도핑 기술을 이용한 아크릴산 생산용 글리세롤 산화탈수반응 촉매 및 일산화탄소 수소화 촉매 개발-
dc.contributor.AlternativeAuthorYang Sik Yun-
dc.contributor.affiliation공과대학 화학생물공학부-
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College of Engineering/Engineering Practice School (공과대학/대학원)Dept. of Chemical and Biological Engineering (화학생물공학부)Theses (Ph.D. / Sc.D._화학생물공학부)
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