Applications of Metal-Organic Frameworks and Their Derived Materials

 
 
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Metal-organic frameworks (MOFs) are porous crystalline polymers con-structed by metal sites and organic building blocks. Since the discovery of MOFs in the 1990s, they have received tremendous research attention for various applications due to their high surface area, controllable mor-phology, tunable chemical properties, and multifunctionalities, including MOFs as precursors and self-sacrificing templates for synthesizing metal oxides, heteroatom-doped carbons, metal-atoms encapsulated carbons, and others. Thus, awareness and knowledge about MOFs and their derived nanomaterials with conceptual understanding are essential for the advanced material community.

This breakthrough new volume aims to explore down-to-earth applications in fields such as bio-medical, environmental, energy, and electronics. This book provides an overview of the structural and fundamental properties, synthesis strate-gies, and versatile applications of MOFs and their derived nanomaterials. It gives an updated and comprehensive account of the research in the field of MOFs and their derived nanomaterials.

Whether as a reference for industry professionals and nanotechnologists or for use in the classroom for graduate and postgraduate students, faculty members, and research and development specialists working in the area of inorganic chemistry, materials science, and chemical engineering, this is a must-have for any library.
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John Wiley & Sons Inc
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978-1-119-65095-9 (9781119650959)
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Inamuddin, PhD, is an assistant professor at King Abdulaziz University, Jeddah, Saudi Arabia and is also an assistant professor in the Department of Applied Chemistry, Aligarh Muslim University, Aligarh, India. He has published about 150 research articles in various international scientific journals, 18 book chapters, and 60 edited books with multiple well-known publishers.

Rajender Boddula, PhD, is currently working for the Chinese Academy of Sciences President's International Fellowship Initiative (CAS-PIFI) at the National Center for Nanoscience and Technology (NCNST, Beijing). He has numerous honors, book chapters, and academic papers to his credit and is an editorial board member and a referee for several reputed international peer-reviewed journals.

Mohd Imran Ahamed, PhD, received his PhD from Aligarh Muslim University, Aligarh, India in 2019. He has published several research and review articles in various international scientific journals, and his research work includes ion-exchange chromatography, wastewater treatment, and analysis, bending actuator and electrospinning.

Abdullah M. Asiri is the Head of the Chemistry Department at King Abdulaziz University and the founder and Director of the Center of Excellence for Advanced Materials Research (CEAMR). He is the Editor-in-Chief of the King Abdulaziz University Journal of Science. He has received numerous awards, and serves on the editorial boards of multiple scientific journals and is the Vice President of the Saudi Chemical Society (Western Province Branch). He holds multiple patents, has authored ten books, more than one thousand publications in international journals, and multiple book chapters.
Preface xiii

1 Application of MOFs and Their Derived Materials in Sensors 1
Yong Wang, Chang Yin and Qianfen Zhuang

1.1 Introduction 1

1.2 Application of MOFs and Their Derived Materials in Sensors 3

1.2.1 Optical Sensor 3

1.2.1.1 Colorimetric Sensor 3

1.2.1.2 Fluorescence Sensor 7

1.2.1.3 Chemiluminescent Sensor 11

1.2.2 Electrochemical Sensor 13

1.2.2.1 Amperometric Sensor 13

1.2.2.2 Impedimetric, Electrochemiluminescence, and Photoelectrochemical Sensor 16

1.2.3 Field-Effect Transistor Sensor 19

1.2.4 Mass-Sensitive Sensor 21

1.3 Conclusion 22

Acknowledgments 23

References 23

2 Applications of Metal-Organic Frameworks (MOFs) and Their Derivatives in Piezo/Ferroelectrics 33
H. Manjunatha, K. Chandra Babu Naidu, N. Suresh Kumar, Ramyakrishna Pothu and Rajender Boddula

2.1 Introduction 34

2.1.1 Brief Introduction to Piezo/Ferroelectricity 34

2.2 Fundamentals of Piezo/Ferroelectricity 34

2.3 Metal-Organic Frameworks for Piezo/Ferroelectricity 40

2.4 Ferro/Piezoelectric Behavior of Various MOFs 40

2.5 Conclusion 52

References 53

3 Fabrication and Functionalization Strategies of MOFs and Their Derived Materials "MOF Architecture" 63
Demet Ozer

3.1 Introduction 63

3.2 Fabrication and Functionalization of MOFs 65

3.2.1 Metal Nodes 65

3.2.2 Organic Linkers 68

3.2.3 Secondary Building Units 76

3.2.4 Synthesis Methods 77

3.2.4.1 Hydrothermal and Solvothermal Method 77

3.2.4.2 Microwave Synthesis 78

3.2.4.3 Electrochemical Method 80

3.2.4.4 Mechanochemical Synthesis 81

3.2.4.5 Sonochemical (Ultrasonic Assisted) Method 81

3.2.4.6 Diffusion Method 82

3.2.4.7 Template Method 82

3.2.5 Synthesis Strategies 83

3.3 MOF Derived Materials 89

3.4 Conclusion 90

References 90

4 Application of MOFs and Their Derived Materials in Molecular Transport 101
Arka Bagchi, Partha Saha, Arunima Biswas and SK Manirul Islam

4.1 Introduction 102

4.2 MOFs as Nanocarriers for Membrane Transport 102

4.2.1 MIL-89 103

4.2.2 MIL-88A 103

4.2.3 MIL-100 104

4.2.4 MIL-101 104

4.2.5 MIL-53 104

4.2.6 ZIF-8 104

4.2.7 Zn-TATAT 105

4.2.8 BioMOF-1 (Zn) 105

4.2.9 UiO (Zr) 105

4.3 Conclusion 106

References 106

5 Role of MOFs as Electro/-Organic Catalysts 109
Manorama Singh, Ankita Rai, Vijai K. Rai, Smita R. Bhardiya and Ambika Asati

5.1 What Is MOFs 109

5.2 MOFs as Electrocatalyst in Sensing Applications 111

5.3 MOFs as Organic Catalysts in Organic Transformations 114

5.4 Conclusion and Future Prospects 115

References 116

6 Application of MOFs and Their Derived Materials in Batteries 121
Rituraj Dutta and Ashok Kumar

6.1 Introduction 122

6.2 Metal-Organic Frameworks 126

6.2.1 Classification and Properties of Metal-Organic Frameworks 127

6.2.2 Potential Applications of MOFs 130

6.2.3 Synthesis of MOFs 133

6.3 Polymer Electrolytes 135

6.3.1 Historical Perspectives and Classification of Polymer Electrolytes 136

6.3.2 MOF Based Polymer Electrolytes 139

6.4 Ionic Liquids 142

6.4.1 Properties of Ionic Liquids 143

6.4.2 Ionic Liquid Incorporated MOF 145

6.5 Ion Transport in Polymer Electrolytes 147

6.5.1 General Description of Ionic Conductivity 147

6.5.2 Models for Ionic Transport in Polymer Electrolytes 148

6.5.3 Impedance Spectroscopy and Ionic Conductivity Measurements 152

6.5.4 Concept of Mismatch and Relaxation 155

6.5.5 Scaling of ac Conductivity 156

6.6 IL Incorporated MOF Based Composite Polymer Electrolytes 157

6.7 Conclusion and Perspectives 166

References 168

7 Fine Chemical Synthesis Using Metal-Organic Frameworks as Catalysts 177
Aasif Helal

7.1 Introduction 177

7.2 Oxidation Reaction 179

7.2.1 Epoxidation 179

7.2.2 Sulfoxidation 181

7.2.3 Aerobic Oxidation of Alcohols 182

7.3 1,3-Dipolar Cycloaddition Reaction 183

7.4 Transesterification Reaction 183

7.5 C-C Bond Formation Reactions 184

7.5.1 Heck Reactions 184

7.5.2 Sonogashira Coupling 186

7.5.3 Suzuki Coupling 186

7.6 Conclusion 187

References 187

8 Application of Metal Organic Framework and Derived Material in Hydrogenation Catalysis 193
Tejaswini Sahoo, Jagannath Panda, Jnana Ranjan Sahu and Rojalin Sahu

8.1 Introduction 193

8.1.1 The Active Centers in Parent MOF Materials 195

8.1.2 The Active Centers in MOF Catalyst 195

8.1.3 Metal Nodes 196

8.2 Hydrogenation Reactions 197

8.2.1 Hydrogenation of Alpha-Beta Unsaturated Aldehyde 197

8.2.2 Hydrogenation of Cinnamaldehyde 198

8.2.3 Hydrogenation of Nitroarene 199

8.2.4 Hydrogenation of Nitro Compounds 201

8.2.5 Hydrogenation of Benzene 202

8.2.6 Hydrogenation of Quinoline 205

8.2.7 Hydrogenation of Carbon Dioxide 206

8.2.8 Hydrogenation of Aromatics 207

8.2.9 Hydrogenation of Levulinic Acid 207

8.2.10 Hydrogenation of Alkenes and Alkynes 208

8.2.11 Hydrogenation of Phenol 210

8.3 Conclusion 210

References 211

9 Application of MOFs and Their Derived Materials in Solid-Phase Extraction 219
Adrian Gutierrez-Serpa, Ivan Taima-Mancera, Jorge Pasan, Juan H. Ayala and Veronica Pino

9.1 Solid-Phase Extraction 220

9.1.1 Materials in SPE 223

9.2 MOFs and COFs in Miniaturized Solid-Phase Extraction ( SPE) 225

9.3 MOFs and COFs in Miniaturized Dispersive Solid-Phase Extraction (D- SPE) 232

9.4 MOFs and COFs in Magnetic-Assisted Miniaturized Dispersive Solid-Phase Extraction (m-D- SPE) 239

9.5 Concluding Remarks 249

Acknowledgments 249

References 249

10 Anticancer and Antimicrobial MOFs and Their Derived Materials 263
Nasser Mohammed Hosny

10.1 Introduction 263

10.2 Anticancer MOFs 264

10.2.1 MOFs as Drug Carriers 264

10.2.2 MOFs in Phototherapy 269

10.3 Antibacterial MOFs 272

10.4 Antifungal MOFs 278

References 280

11 Theoretical Investigation of Metal-Organic Frameworks and Their Derived Materials for the Adsorption of Pharmaceutical and Personal Care Products 287
Jagannath Panda, Satya Narayan Sahu, Tejaswini Sahoo, Biswajit Mishra, Subrat Kumar Pattanayak and Rojalin Sahu

11.1 Introduction 288

11.2 General Synthesis Routes 290

11.2.1 Hydrothermal Synthesis 295

11.2.2 Solvothermal Synthesis of MOFs 296

11.2.3 Room Temperature Synthesis 296

11.2.4 Microwave Assisted Synthesis 296

11.2.5 Mechanochemical Synthesis 297

11.2.6 Electrochemical Synthesis 297

11.3 Postsynthetic Modification in MOF 297

11.4 Computational Method 297

11.5 Results and Discussion 299

11.5.1 Binding Behavior Between MIL-100 With the Adsorbates (Diclofenac, Ibuprofen, Naproxen, and Oxybenzone) 299

11.6 Conclusion 303

References 304

12 Metal-Organic Frameworks and Their Hybrid Composites for Adsorption of Volatile Organic Compounds 313
Shella Permatasari Santoso, Artik Elisa Angkawijaya, Vania Bundjaja, Felycia Edi Soetaredjo and Suryadi Ismadji

12.1 Introduction 314

12.2 VOCs and Their Potential Hazards 315

12.2.1 Other Sources of VOCs 319

12.3 VOCs Removal Techniques 320

12.4 Fabricated MOF for VOC Removal 324

12.4.1 MIL Series MOFs 325

12.4.2 Isoreticular MOFs 327

12.4.2.1 Adsorption Comparison of the Isoreticular MOFs 330

12.4.3 NENU Series MOFs 332

12.4.4 MOF-5, Eu-MOF, and MOF-199 333

12.4.5 Amine-Impregnated MIL-100 334

12.4.6 Biodegradable MOFs MIL-88 Series 335

12.4.7 Catalytic MOFs 335

12.4.8 Photo-Degradating MOFs 336

12.4.9 Some Other Studied MOFs 337

12.5 MOF Composites 338

12.5.1 MIL-101 Composite With Graphene Oxide 338

12.5.2 MIL-101 Composite With Graphite Oxide 338

12.6 Generalization Adsorptive Removal of VOCs by MOFs 340

12.7 Simple Modeling the Adsorption 340

12.7.1 Thermodynamic Parameters 340

12.7.2 Dynamic Sorption Methods 341

12.8 Factor Affecting VOCs Adsorption 344

12.8.1 Breathing Phenomena 344

12.8.2 Activation of MOFs 345

12.8.3 Applied Pressure 346

12.8.4 Relative Humidity 347

12.8.5 Breakthrough Conditions 347

12.8.6 Functional Group of MOFs 347

12.8.7 Concentration, Molecular Size, and Type of VOCs 348

12.9 Future Perspective 349

References 350

13 Application of Metal-Organic Framework and Their Derived Materials in Electrocatalysis 357
Gopalram Keerthiga, Peramaiah Karthik and Bernaurdshaw Neppolian

List of Abbreviations 358

13.1 Introduction 358

13.2 Perspective Synthesis of MOF , and Their Derived Materials 360

13.3 MOF for Hydrogen Evolution Reaction 362

13.4 MOF for Oxygen Evolution Reaction 363

13.5 MOF for Oxygen Reduction Reaction 365

13.6 MOF for CO2 Electrochemical Reduction Reaction 366

13.6.1 Electrosynthesis of MOF for CO2 Reduction 366

13.6.2 Composite Electrodes as MOF for CO2 Reduction 367

13.6.3 Continuous Flow Reduction of CO2 369

13.6.4 CO2 Electrochemical Reduction in Ionic Liquid 369

13.7 MOF for Electrocatalytic Sensing 370

13.8 Electrocatalytic Features of MOF 371

13.9 Conclusion 372

Acknowledgment 372

References 372

14 Applications of MOFs and Their Composite Materials in Light-Driven Redox Reactions 377
Elizabeth Rojas-Garcia, Jose M. Barrera-Andrade, Elim Albiter, A. Marisela Maubert and Miguel A. Valenzuela

14.1 Introduction 378

14.1.1 MOFs as Photocatalysts 381

14.1.2 Charge Transfer Mechanisms 382

14.1.3 Methods of Synthesis 385

14.2 Pristine MOFs and Their Application in Photocatalysis 387

14.2.1 Group 4 Metallic Clusters 387

14.2.2 Groups 8, 9, and 10 Metallic Clusters 393

14.2.3 Group 11 Metallic Clusters 393

14.2.4 Group 12 Metallic Clusters 403

14.3 Metal Nanoparticles-MOF Composites and Their Application in Photocatalysis 413

14.3.1 Ag-MOF Composites 415

14.3.2 Au-MOF Composites 417

14.3.3 Cu-MOF Composites 417

14.3.4 Pd-MOF Composites 418

14.3.5 Pt-MOF Composites 419

14.4 Semiconductor-MOF Composites and Their Application in Photocatalysis 421

14.4.1 TiO2-MOF Composites 422

14.4.2 Graphitic Carbon Nitride-MOF Composites 426

14.4.3 Bismuth-Based Semiconductors 429

14.4.4 Reduced Graphene Oxide-MOF Composites 430

14.4.5 Silver-Based Semiconductors 436

14.4.6 Other Semiconductors 438

14.5 MOF-Based Multicomponent Composites and Their Application in Photocatalysis 442

14.5.1 Semiconductor-Semiconductor-MOF Composites 442

14.5.2 Semiconductor-Metal-MOF Composites 443

14.6 Conclusions 446

References 448

Index 463

1
Application of MOFs and Their Derived Materials in Sensors


Yong Wang1,2*, Chang Yin1 and Qianfen Zhuang1

1College of Chemistry, Nanchang University, Nanchang, China

2Jiangxi Province Key Laboratory of Modern Analytical Science, Nanchang University, Nanchang, China

Abstract
In the past years, the application of metal organic framework (MOFs) and their derived materials in sensors has attracted wide attention due to their outstanding physical and chemical properties such as large specific surface area, tunable pore size, easy design/functionalization, high stability, good catalytic ability, and so on. In this chapter, we present some recent progress in the sensing field of MOFs and their derived materials. Depending on the signal transduction mechanism, different types of sensors are outlined. Moreover, the present problems and future development of MOFs and their derived materials are also presented.

Keywords: Metal organic framework, derived materials, sensor

1.1 Introduction


Sensor is a material or device that measures a physical or chemical quantity and converts it into an observable signal for detection of specific chemicals at trace levels [1-3]. Generally, sensing-based detection methods are superior to those traditional detection methods such as titration, chromatography, mass spectrometry and so on, because of its rapidity, simplicity, low cost, and suitability for large-scale sample screening [1-3]. On the basis of these advantages, the sensing-based approaches have been widely used in fields of environmental and industrial monitoring, drug quality monitoring, forensic analysis, food safety, medical diagnostics, and national security [1-3]. However, at present, sensors suffer from some disadvantages like poor sensitivity, limited selectivity, slow response time, low lifetime, and stability.

To over these limitations, many advanced materials have been developed to construct various robust sensors [4-10]. Among them, metal- organic frameworks (MOFs) are especially attractive as a novel sensing material [11-18]. This material is a kind of crystalline material possessing nanopore network structure, which are formed by self-assembly of coordination between transition-metal cations and oxygen or nitrogen-containing polydentate organic linkers (see Figure 1.1) [19].

Generally, the large specific surface area of MOFs improves sensor sensitivity [11-18]. The metal ions or polydentate ligands of MOFs can be rationally designed to modulate the pore size of MOF, the number and orientation of catalytically active sites of MOFs, and the different interaction force between the analyte and MOF receptor, which enhance the sensor selectivity and sensitivity [11-18]. In addition, the interaction force and the structural matching between the analyte and MOF receptors can be modulated to increase the reversibility and response time of the sensor toward analyte, leading to the regeneration and real-time monitoring of the sensor [11-18]. On the other hand, MOF-derived materials are usually obtained using MOFs and/or other materials as precursors by various strategies such as high-temperature calcinations, hydrothermal synthesis, solvothermal synthesis, and so on [20-25]. These derived materials can not only retain the original structure of MOFs, but also improve some performances of these materials like electric conductivity, stability, water-solubility, catalytic activity, and mass-transfer ability [20-25]. These merits from the MOF-derived materials lead to the enhancement of the sensor's performances.

Figure 1.1 (a)-(c) Inorganic secondary building units (SBUs) of MOFs. (d)-(f) Organic ligands of MOFs.

Reproduced with permission from Ref. [19]. Copyright 2004 Elsevier.

In the chapter, four different types of sensor, namely, optical sensor, electrochemical sensor, field-effect transistor-based sensor, and mass-sensitive sensor, is respectively described on the basis of the signal transduction mechanism. Particularly, we focus on the use of MOFs and their derived materials in the construction of sensors for detection of analyte, and summarize some representative investigations on the use of MOFs and their derived materials in the above-mentioned four types of sensor.

1.2 Application of MOFs and Their Derived Materials in Sensors


1.2.1 Optical Sensor


Optical sensor has recently attracted wide attention owing to its operation simplicity, time efficiency, and good reproducibility. MOFs and their derived materials can be easily designed to introduce optical probes, facilitating the construction of optical sensor. In addition, MOFs and their derived materials are demonstrated to possess nanozyme activity, which can catalyze various substrates into optical substances. As a result, the nanomaterials with artificial enzymes can be conveniently combined with different optical substances to construct various optical sensors. On the basis of optical transduction mechanism, optical sensors are usually classified into three types: colorimetric sensors, fluorescent sensors, chemiluminescent sensors. Therefore, the three different types of optical sensors will be introduced in the following section.

1.2.1.1 Colorimetric Sensor

In 2013, Li's group synthesized a Fe-MIL-88NH2 MOF using 2-aminoterephthalic acid and FeCl3 as precursors in a medium of acetic acid, and found for the first time that the MOF acted as a peroxidase, and could catalyze the oxidation of 3,3´,5,5´-tetramethylbenzidine (TMB) by H2O2 to produce a blue product [26]. Subsequently, they combined the MOF materials with glucose oxidase to construct a sensitive colorimetric sensor for glucose detection (see Figure 1.2) [26]. Following the work, many researchers exploited the peroxidase-like activity of the MOFs and their derived materials to construct various colorimetric sensor. Tan et al. [27] prepared a nanocomposite (CuNPs@C) composed of copper nanoparticles dispersed in a carbon matrix by one-pot thermal decomposition of a copper-based MOF precursor. The CuNPs@C can also possess peroxidase-like activity, which catalyze the reaction between H2O2 and 3,3,5,5-tetramethyl-benzidine (TMB). Because this CuNPs surface does not contain a stabilizer, a higher affinity of CuNPs@C toward H2O2 can be obtained. Depending on the inhibition of TMB oxidation by ascorbic acid (AA), the material can be used to construct a colorimetric quenching sensor for detecting AA. Hou et al. used magnetic zeolitic imidazolate framework 8 to pack glucose oxidase, and then constructed the nanocomposite-based colorimetric sensor for glucose [28]. Dong et al. [29] encapsulated cobalt nanoparticles into Fe MOF-derived magnetic carbon to produce a nanocomposite, and found that the nanocomposite had much stronger peroxidase-like activity than pure CoNPs and magnetic carbon. Therefore, they combined glucose oxidase with the CoNPs/MC to construct a robust glucose sensor.

Metal ions are present in the ecosystem, and have important influence on the ecosystem. Hence, the construction of sensor for detection of metal ions is necessary for industrial processes, medical diagnosis, and environmental monitoring. In 2015, Gao et al. [30] synthesized a thermostable magnesium metal-organic framework (Mg-MOF), and found that many nanoholes containing non-coordinating nitrogen atoms were present in the material, which is suitable for hosting Eu3+ ions. On the basis of the energy level matching and energy transfer between the Eu3+ and the Mg-MOF, they constructed a sensitive sensor for detection of Eu3+ ions. Khalil et al. [31] used UiO-66 metal-organic frameworks to accommodate diethyldithiocarbamate (DDTC) chromophore, and the obtained DDTC/UiO-66 was used for the construction of digital image-based colorimetric sensor for Cu2+ detection. Zeng et al. [32] synthesized bimetallic (Eu-Tb) lanthanide (Ln) metal-organic frameworks (MOFs) using Tb3+/Eu3+ and 1,4-benzenedicarboxylate (BDC) as precursors for on-site sensitive and selective detection of Pb2+ in environmental waters. Li et al. [33] synthesized a composite containing Pt nanoparticle and UiO-66-NH2 with permanent porosity, strong thermal and high chemical stability, and found that the material displayed high peroxidase-like activity. However, the peroxidase-like behavior of the material was suppressed in the presence of Hg2+, due to the Hg2+/Pt nanoparticle specific interaction. Therefore, they followed the principle to realize the construction of Hg2+ sensor (see Figure 1.3).

Figure 1.2 Schematic illustration of the peroxidase-like activity of Fe-MIL-88NH2 MOFs using TMB and H2O2 as reactants and their applications for glucose sensing.

Reproduced from Ref. [26] with permission. Copyright 2013 Royal Society of Chemistry.

Recently, Wang et al. [34] has exploited the partial oxidation of cerium(III) to prepare the mixed-valence state cerium-based metal-organic framework (MVC-MOF) with the oxidase activity, and demonstrated that the oxidase activity of the MVC-MOF could be suppressed by single-stranded DNA (ssDNA). However, the oxidase activity of the material can be prevented in the presence of double-stranded DNA (dsDNA)....

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