Inorganic Micro- and Nanomaterials (eBook)

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Michele Aresta, University of Bari, Italy; Angela Dibenedetto, University of Bari, Italy.

Introduction: Nano- (and micro-)materials and human wellbeing 15
1 Coating antibacterial nanoparticles on textiles: Towards the future hospital in which all textiles will be antibacterial 17
1.1 Introduction: Application of nanotechnology for “smart” textiles 17
1.2 Sonochemical method for the synthesis of nanostructured materials and their adherence to solid substrates 20
1.3 Ultrasound assisted deposition of metal nano-oxides on textiles and their antibacterial properties 22
1.3.1 Synthesis and deposition of CuO nanoparticles 22
1.3.2 Finishing of textiles with crystalline TiO2 nanoparticles via a one-step process 24
1.3.3 Synthesis and deposition of ZnO 30
1.3.4 Enzymatic pretreatment as a means of enhancing antibacterial activity and stability of ZnO nanoparticles sonochemically coated on cotton fabrics 36
1.3.5 Size dependence of the antibacterial activity of ZnO NPs 42
1.4 Conclusion 42
Bibliography 43
2 Automated solutions for high-throughput experimentation in heterogeneous catalyst research 49
2.1 Introduction 49
2.2 The preparation of solid catalysts 51
2.3 Automation challenges examples 51
2.3.1 Integration of commercially available devices 52
2.4 A fully-automated solution 53
2.4.1 SOPHAS-CAT HT 53
2.4.2 The loading 53
2.4.3 The synthesizer 54
2.4.4 Extrudate preparation 55
2.4.5 Impregnation and drying 55
2.4.6 Calcination 56
2.4.7 Scraping and pelletizing 56
2.4.8 Grinding 57
2.4.9 Sieving 57
2.5 Conclusion 58
Bibliography 59
3 Insights from XPS on nanosized inorganic materials 61
3.1 Introduction 61
3.2 XPS in the nanodomain 61
3.3 Conclusions 67
Bibliography 69
4 Single crystal and powder XRD techniques: An overview 71
4.1 The single crystal XRD technique 71
4.1.1 Basics of the radiation-matter interaction 72
4.1.2 Basics of crystallography and X-ray diffraction by crystal 75
4.1.3 Solving the phase problem by direct methods 83
4.2 The powder XRD technique 88
4.2.1 Indexation 88
4.2.2 Space group determination 90
4.2.3 Profile decomposition and intensity extraction 91
4.2.4 Structure solution 93
4.2.5 Rietveld refinement 98
4.2.6 Examples 99
4.3 Conclusions 102
Bibliography 103
5 Structural and electronic characterization of nanosized inorganic materials by X-ray absorption spectroscopies 107
5.1 Introduction 107
5.2 XAS spectroscopy: Basic background 107
5.2.1 Theoretical background of XAS spectroscopy 108
5.2.2 The XANES region 110
5.2.3 The EXAFS region 110
5.2.4 Advantages and drawbacks of the technique 113
5.3 CuCl2/Al2O3-based catalysts for ethylene oxychlorination 114
5.3.1 Industrial relevance of the CuCl2/Al2O3 system 114
5.3.2 Preliminary in situ XAFS experiments 115
5.3.2.1 The determination of the Cu-aluminate phase: How to avoid possible pitfalls in the EXAFS data analysis 115
5.3.2.2 Catalyst reactivity with the separate reactants: In situ XAFS experiments 117
5.3.3 Operando experiments and criteria used to face the presence of more than one phase in the sample 119
5.4 Structural and electronic configuration of Cp2Cr molecules encapsulated in PS and Na-Y zeolite and their reactivity towards CO 123
5.4.1 Structure of Cp2Cr encapsulated in PS and Na-Y zeolite matrices 123
5.4.2 Determination of the electronic structure of Cp2Cr by combined UV-Vis and XANES spectroscopies 125
5.4.3 Reactivity of Cp2Cr hosted in PS and in Na-Y zeolite towards CO: IR and XAFS results 128
5.5 Transition metal complexes in solution: The [cis-Ru(bpy)2(py)2]2+ case study 131
5.5.1 Structure refinement of cis-[Ru(bpy)2(py)2]2+ in aqueous solution by EXAFS spectroscopy 132
5.5.2 Advanced details of the EXAFS structure refinement of cis-[Ru(bpy)2(py)2]2+ complex 134
5.6 EXAFS study on MOFs of the UiO-66/UiO-67 family: comparison with XRPD and ab initio investigations 136
5.7 Applications of X-ray micro beams: Electroabsorption modulated laser for optoelectronic devices 141
Bibliography 143
6 Lens-less scanning X-ray microscopy with SAXS and WAXS contrast 151
6.1 Introduction 151
6.2 X-ray microscopes 152
6.3 Small-angle and wide-angle scattering contrast (SAXS and WAXS) 157
6.4 Applications 163
Bibliography 168
7 Characterization of inorganic nanostructured materials by electron microscopy 171
7.1 Introduction 171
7.2 Electron microscopy 172
7.2.1 Working principles 173
7.3 Scanning electron microscopy 175
7.3.1 Magnification and resolution of SEM 177
7.3.2 Interaction of the electron beam with the sample: elastic and inelastic scattering 177
7.3.2.1 Secondary electrons and their detection 178
7.3.2.2 Backscattered electrons and their detection 180
7.3.2.3 Energy loss 181
7.4 Transmission electron microscopy 181
7.4.1 The instrument 182
7.4.2 Image formation process 183
7.5 Sample preparation for electron microscopy 188
7.5.1 SEM sample preparation 188
7.5.1.1 Casting 188
7.5.1.2 Ion sputtering 189
7.5.2 Sample preparation for TEM 189
7.6 Inorganic nanocrystal investigation by SEM 191
7.7 Inorganic nanocrystal investigation by TEM 200
7.7.1 Bright field mode 200
7.7.2 Dark field contrast mode 203
7.7.3 Diffraction mode – electron diffraction 204
7.7.3.1 Selected area diffraction 205
7.7.3.2 Convergent beam electron diffraction 205
7.7.3.3 Investigating crystalline structure: High-resolution TEM 206
7.8 Chemical analysis by electron microscopy 207
7.8.1 Energy dispersion spectroscopy (EDS) 207
7.8.2 Electron energy loss spectroscopy (EELS) 208
7.8.3 Energy-filtered transmission electron microscopy (EFTEM) 209
7.8.4 Some examples of chemical analysis in electron microscopy 209
7.9 Conclusions 211
Bibliography 211
8 Nanosized particles: questioned for their potential toxicity, but some are applied in biomedicine 213
8.1 Introduction 213
8.2 Nanoparticles classification 213
8.3 Nanoparticles and biosystems 215
8.4 Stability and toxicity 216
8.5 Fields of application of engineered nanoparticles 217
8.6 Access to bio-organisms and toxicity to organisms 218
8.7 Applications of nanoparticles in biomedicine 219
8.8 Measurement of the concentration 220
8.9 Conclusions 220
Bibliography 221
Index 225