Metal Semiconductor Core-shell Nanostructures for Energy and Environmental Applications

Metal Semiconductor Core–Shell Nanostructures for Energy and Environmental Applications

Edited by

Raju Kumar Gupta

Department of Chemical Engineering

Indian Institute of Technology Kanpur, India

Mrinmoy Misra

Department of Chemical Engineering

Indian Institute of Technology Kanpur, India

Table of Contents

Cover

Title page

Copyright

Dedication

List of Contributors

Editor Biographies

Preface

Chapter 1: Introduction to semiconductor nanomaterial and its optical and electronics properties

Abstract

1.1. Introduction

1.2. Classification of nanostructured materials

1.3. Core–shell nanostructured materials

1.4. Semiconductor core–shell nanomaterials

1.5. Properties of nanostructured core–shell materials

1.6. Synthesis of core–shell nanomaterials

1.7. Applications of nanostructured core–shell materials

1.8. Conclusions

Chapter 2: Core–shell nanostructures: an insight into their synthetic approaches

Abstract

2.1. Introduction

2.2. Methods

Chapter 3: Characterization of metal, semiconductor, and metal-semiconductor core–shell nanostructures

Abstract

3.1. Introduction

3.2. Microscopic characterization

3.3. Spectroscopic characterization

3.4. Optical characterization

3.5. Other spectroscopic characterization

3.6. Conclusions

Acknowledgment

Chapter 4: Metal/semiconductor core/shell nanostructures for environmental remediation

Abstract

4.1. Introduction

4.2. Basic science in photocatalysis process

4.3. Environmental application of metal/semiconductor core/shell nanoparticles

4.4. Metal/semiconductor core/shell nanoparticles in environment purification

4.5. Concluding remarks and future prospective

Chapter 5: Metal-semiconductor core–shell nanomaterials for energy applications

Abstract

5.1. Energy and environment

5.2. Electrochemical energy storage and conversion devices

5.3. Role of nanomaterials in supercapacitors, fuel cells and lithium ion batteries applications

5.4. Metal-semiconductor core–shell nanomaterials for energy storage and conversion

5.5. Correlation between electronic structure and electrochemical activity of core–shell nanomaterials

5.6. Future outlook and challenges

Acknowledgements

Chapter 6: Metal-semiconductor core–shell nanostructured photocatalysts for environmental applications and their recycling process

Abstract

6.1. Introduction

6.2. Different nanostructured nanoparticles:

6.3. Core–shell nanoparticles

6.4. Metal–metal oxide core–shell nanoparticle synthesis

6.5. Photocatalysis

6.6. Mechanism of heterogeneous phtotocatalysis by core–shell nanostructures

6.7. Wastewater treatment by core–shell nanostructured photocatalysts

6.8. Inactivation of microorganisms and air purification

6.9. Other applications

6.10. Photocatalytic reactor design and recycling of core–shell nanoparticle photocatalysts

6.11. Conclusions and outlooks

Acknowledgment

Chapter 7: Metal and metal-semiconductor core–shell nanostructures for plasmonic solar cell applications

Abstract

7.1. Introduction

7.2. Applications of core–shell metal semiconductor nanoparticles in different solar cells

7.3. Bimetallic core–shell nanoparticles for plasmonic solar cell

7.4. Conclusions

Chapter 8: Core–shell nanostructures as a platform for sensing applications

Abstract

8.1. Introduction

8.2. Classification of core–shell-based nanosensors

8.3. Conclusions

Acknowledgments

Index

Copyright

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Dedication

To my parents and teachers, who helped me become what I am today.

Raju Kumar Gupta

I would like to thank all my contributors for their enthusiasm and support in producing this book. I hope that you, the readers, will find this book useful to undertake further research in photo catalysis and solar cell to directly contribute to this exciting and interdisciplinary research field.

Mrinmoy Misra

List of Contributors

Vasudha Bansal,     Center of Innovative and Applied Bioprocessing, Mohali, India

Ashok N. Bhaskarwar,     Indian Institute of Technology, Delhi, India

Mickael Castro,     SmartPlastics Group, Bretagne Loire University, Lorient, France

Rajib Ghosh Chaudhuri,     Birla Institute of Technology and Science, Pilani, Dubai, United Arab Emirates

Jean-Francois Feller,     SmartPlastics Group, Bretagne Loire University, Lorient, France

Raju Kumar Gupta,     Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India

Jyoti,     Central Scientific Instruments Organisation (CSIR-CSIO), Chandigarh, India

Vishaldeep Kaur,     Central Scientific Instruments Organisation (CSIR-CSIO), Chandigarh, India

Ki-Hyun Kim,     Hanyang University, Seoul, Republic of Korea

Naresh Kumar,     UIET Punjab University, Chandigarh, Punjab, India

Nishant Kumar,     Central Scientific Instruments Organisation (CSIR-CSIO), Chandigarh, India

Pawan Kumar,     Central University of Jammu, Jammu, India

Mrinmoy Misra,     Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India

Pallabi Moitra,     The University of Burdwan, Burdwan, West Bengal, India

Kunal Mondal,     North Carolina State University, Raleigh, NC, United States

Rupali Nagar,     Symbiosis Institute of Technology, Symbiosis International University, Pune, Maharashtra, India

Manoj K. Nayak

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Vidhu S. Pandey

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Rahul Ranjan,     Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India

Baljit Singh

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Jaswant Singh

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Narendra Singh,     Indian Institute of Technology Kanpur, Kanpur, Uttar Pradesh, India

Suman Singh,     Central Scientific Instruments Organisation (CSIR-CSIO), Chandigarh, India

Shilpa Soni

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Sumit K. Sonkar,     Malaviya National Institute of Technology, Jaipur, Rajasthan

Kumud M. Tripathi,     SmartPlastics Group, Bretagne Loire University, Lorient, France

Sachin Tyagi

Academy of Innovative and Scientific Research (AcSIR)-CSIO

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Bhaghavathi P. Vinayan

Helmholtz Institute Ulm (HIU) for Electrochemical Energy Storage, Ulm

Karlsruhe Institute of Technology (KIT), Karlsruhe, Germany

Editor Biographies

Raju Kumar Gupta is an Assistant Professor at the Department of Chemical Engineering, Indian Institute of Technology Kanpur, India. He graduated with a PhD from National University of Singapore (NUS), Singapore. He has received several awards, such as DST Inspire Faculty Award 2013, IAAM Young Scientist Award 2014, and IEI Young Engineer Award (2014–2015). His research interests include surface chemistry, green synthesis of nanomaterials, high dielectric constant materials, polymer, and polymer-inorganic hybrid materials for electric energy storage, hybrid perovskite solar cells, electrospinning of functional polymers, and nanocomposites for environmental and energy applications. A member of several international journal editorial boards, Dr. Gupta has authored more than 30 research articles in SCI journals, 2 books, and 7 book chapters.

Mrinmoy Misra is a postdoctoral fellow at the Department of Chemical Engineering, Indian Institute of Technology Kanpur, India. He graduated with a PhD from Academy of Scientific & Innovative Research, India. He has received awards such as Indian Institute of Technology Kanpur postdoctoral fellowship, 2015, Award of science & engineering research board (SERB) National Post-Doctoral fellowship, 2016. His research interests include thin-film fabrication, nanomaterial based senor, photo catalytic materials, nanoparticle synthesis, and characterization and solar cells. Dr. Misra has authored eight research articles in SCI journals. He has also delivered papers at several international conferences.

Preface

Metal semiconductor core–shell nanostructures for energy deals with organic, dye–sensitized solar cell, water splitting and fuel cell applications. Metal nanomaterials show plasmonic effect and enhanced light absorption. This book discusses the effect of semiconductor shell on metal nanoparticle or vice versa resulting in reduced charge recombination at the interface. The effect of nanoparticles in different layers of solar cells resulting in higher efficiency is discussed. The book also covers the use of different shaped nanoparticles to enhance efficiency in energy conversion and storage applications like solar cells, fuel cells, rechargeable batteries, super capacitors, and so on.

Metal semiconductor core–shell nanostructures for environmental applications deals with the review of the most recent published works in the field of metal semiconductor core–shell nanomaterials for environmental application, recycling process, and possibility of reuse. The book emphasizes different methods for the synthesis of metal semiconductor core–shell nanostructures. Further, the efforts to design core–shell nanomaterials with different physicochemical properties are also discussed.

Chapter 1

Introduction to semiconductor nanomaterial and its optical and electronics properties

Manoj K. Nayak

Jaswant Singh

Baljit Singh

Shilpa Soni

Vidhu S. Pandey

Sachin Tyagi

Academy of Innovative and Scientific Research (AcSIR)-CSIO, India

CSIR-Central Scientific Instruments Organization (CSIO), Chandigarh, India

Abstract

Semiconductor nanoparticles is an important class of nanostructured materials that have a plethora of interesting physical, chemical, mechanical, optical, and electronic, properties. This chapter provides an overview of research pertaining to various nanostructured materials in general and core–shell nanoparticles (CSNs) in particular. Different classification criteria of nanostructured materials based on their sources, dimensions, structural configurations, and nature of core/shell materials have been discussed. Semiconducting core–shell nanoparticles are segregated into different types based on the energy levels of the core and shell materials. Optical and electronic properties of CSNs along with synthesis techniques are discussed in details. Moreover, semiconductor core–shell nanostructure materials highlight the key developments and current status in fields, such as electronic, health, agricultural, food processing, sustainable energy, and environmental catalysis. This chapter covers an introduction to the field of semiconductor and core–shell nanostructures and provides comprehensive understanding to various aspects of these materials in details.

Keywords

core–shell nanoparticles

synthesis and characterization

shape size effect

catalytic activities

photovoltaic

solar cell

LEDs

1.1. Introduction

Clean environment and green energy resources are the basic requirements of every society. Until the 21st century, humans have relied mostly upon the nonrenewable energy sources that degraded the environment significantly. Energy and environment are the major issues in today’s world. Nanotechnology is a branch of engineering that deals with the design and development at the molecular level of matter. Nanotechnology finds application in many products used in everyday life. Nanotechnology is a combination of two words; nano and technology, nano is kind of prefix like micro, milli, or kilo, mega, giga. Nanotechnology basically deals with the collections of techniques, methods, skill, and procedures for the production of materials having a size in range from sub nanometer (nm) to several hundred of nm. A nm is an extremely small unit equivalent to one billionth part of a meter (10−9 m). To have an idea of one nanometer consider 10 hydrogen atoms (each having diameter ∼100 pm) or five silicon atoms (each having diameter ∼200 pm) are arranged along a line. The unique physical and chemical properties of nanomaterials witness their potential for providing innovative solutions to many current problems of modern society. Rapid advances in materials science due to the development of precision instrumentation and characterization techniques have enabled the researchers to understand indepth the nanomaterials at subatomic levels. Clear understanding of molecular levels, structures, particle sizes, and grain boundaries, interaction between grain boundaries, and so on, helps in development of synthesis strategy. It also inspires researchers for development of materials with enhances properties for wide variety of applications at nanoscale level.

This chapter highlights the various types of nanomaterials followed by the detailed description of core–shell nanomaterials and their use in plasmonic and dye sensitized solar cells. It is well known that properties of interfacial material used in cell highly influence the cell performance through the key processes occurring at interface of many practical devices, such as generation, collection, recombination of charges. In this chapter, we unravel recent developments in terms of materials and technologies associated with its functionalization at interface level of engineering for highly efficient dye-sensitized solar cells which are highlighted in the outlook. Furthermore, while emphasizing on dye-sensitised solar cells (DSSCs), it’s elaborate the application of core–shell nanomaterials in various fields like biomedical, agriculture, food processing, and sensing application, and so on.

1.2. Classification of nanostructured materials

Nanostructured materials are made up from the bulk material but have size in range of nm scale (<100 nm). Apart from size, they also differ from the bulk materials in terms of their physical, as well as novel chemical properties. In past decades huge attentions has been given to nanoparticles from the microparticles as the former has unique properties which are not at all present in the latter one. The most common example from these properties of nanomaterials is increase in its surface to volume ratio, which allows the surface atoms of materials to dominate over the interior atoms. The small size of nanomaterials enables the predominance of quantum effects. Although there is not a hard and fast rule to classify the nanostructured materials but broadly they can be classified in following subsections on the basis of factors discussed later.

1.2.1. Source of origin

We can classify the nanomaterials based on their origin into two different categories namely natural and artificial nanostructure materials. Natural nanostructured materials, which are present inside or obtained from the natural resources, are the natural nanomaterials, for example, protein molecules, virus, antibodies, lotus leaf, silk of spider, colloidal solution (like blood and milk), wings of insect, gelatin, and so on are some examples of natural nanomaterials. On the other hand artificial nanostructured materials are those, which does not exist in nature, rather they are synthesized through well-established chemical or mechanical method, for example, carbon nanostructures, graphene, carbon nanotubes, metal oxide, and chalcogenide semiconductor nanoparticles, and so on.

1.2.2. Dimensions

Based on the dimensions the nanostructured materials are majorly classified into zero, one, two, and three-dimensional materials in nature. Zero dimension (0D) nanostructured materials have size in range of nm in all three dimensions [1,2]. Metallic particles like silver and gold nanoparticles are the some of the examples of 0D nanostructured materials in addition to these quantum dots are also considered as perfect example. Normally these are of spherical shape but it indeed varies as cubes and polygons as well. In the case of one dimensional (1D) nanostructured materials, size in one direction is out of nanometre scale. Nanorods, nanowires, carbon nanotubes, and nanocrystal fiber are some examples of 1D nanostructures [3,4]. In two dimensional (2D) nanostructured materials, size is out of nm scale for two directions [5–8]. The film of nanomaterials with thickness in range of nm is best example of such kind of materials. Nanosheets, nanowalls are few more examples, for 2D nanostructured materials. The area of film may extend up to several micrometer but the thickness will remain in nm range. The size of three dimensional (3D) nanostructured materials is out of nanoscale for all 3D. The reason of inclusion of these materials to nanostructured material category is that they made up of individual blocks each having size in nanoscale. Therefore, they can be bundle of nanowires, dispersions of nanoparticles, multinanolayers, and many more [9–13].

1.2.3. Structural configuration

Based on the structural configuration we can classify the nanostructures materials into carbon-based nanomaterials, metal-based nanomaterials, dendrimers, and nanocomposites. As name suggests itself, carbon based nanostructured materials are the one in which carbon is essential element of carbons based nanostructured materials. Carbon nanomaterials have exceptional mechanical, thermal, electrical, and chemical properties, which find a special attention in nanoscience. Carbon nanotubes, carbon nanowires, fullerenes, and graphene are the some example of carbon based nanostructured materials. Whereas, metal based nanostructured materials are those in which constituency of metal is main. They include the nanoparticle of metals and metals oxides, for example, silver nanoparticles, gold nanoparticles, zinc oxide nanoparticles, titanium dioxide nanoparticles, and many more [14–19]. The dendrimers are known as polymeric molecules, spherical in shape with highly branched nanoscale structures. They are formed by the nanoscale hierarchical self-assembly process. Generally, many chains are present on the surface of dendrimers, which owes it for wide variety of application like in drug delivery and removal of heavy metal ion from the water. Nanocomposites are formed from multiple materials (having different physical and chemical properties) which results in novel properties of nanocomposite material which differ from that of individual constituent. Nanocomposite is a multiphase solid material, in which one of the phases has either, one, two, or all three dimensions of less than 100 nm. Colloids, porous media, copolymers, and gels are some of the examples of such materials.

1.3. Core–shell nanostructured materials

Core–shell nanomaterials are composed of two or more materials out of which at least one material acting as a shell which covers the other core material. The core nanoparticles are encapsulated by the shell particles. There can be many shapes of core–shell nanomaterials, the most common shape is circular/spherical core entrapped by a concentric circular/sphere shell as shown later in Fig. 1.1A.

Figure 1.1   (A) TEM image of spherical CoFe2O4/Fe3O4 core–shell nanomaterials from encapsulation [20]; (B) core–shell materials hexagonal configuration of Au nanoparticle/ZIF-8 hybrid crystals [21]; (C) multiple core and single shell core–shell nanomaterials (TEM image of 13 nm Au nanoparticles in ZIF-8 crystals) [21]; (D) moveable core–shell nanomaterials TEM images of Au@SiO2@PBzMA particles after HF etching [22].

Other shapes of core–shell material are being emphasised due to their interactive properties. The nonspherical shapes of core materials will results in shape variation from concentric spheres to nonspherical, for example, hexagonal shape core–shell nanomaterials (Fig. 1.1B). Fig. 1.1C shows, multiple core core–shell materials in which a single material can be used to coat upon more than one core materials the resulting structures are called multiple core core–shell materials.

The core and shell of core–shell material can be separated by the nanoscale dielectric coatings, which will result in the formation of multilayer metallodielectric materials. Metallodiectric materials found importance in nanoscience for their plasmonic properties. In core–shell materials, it is not necessarily that core will always be stationary inside the shell, it can also move inside the shell. Such materials fall under the category of movable core core–shell nanomaterials, as shown in Fig. 1.1D. The moveable core type materials are formed by bilayer coating, and then removing the inner layer with a suitable method in such a way that the shell becomes a hollow structure in which core can move.

Nanomaterials attract the researchers with their potential to address many problems related to environment and energy. Numerous studies have been carried out and reported on the synthesis, characterization, and application of core–shell nanomaterials. Although it’s a very challenging task, to categories the core–shell nanomaterials as they can be differentiated in terms of synthesis methods, edibility, source, end use application, and so on. However, in a broad sense we can categorize core–shell nanomaterials into four types on the basis of core and shell materials. Inorganic or organic materials can be utilized for the synthesis of core–shell nanomaterials. The broad classification of the core–shell nanomaterials can be understood from the Fig. 1.2. These classes are either based on the type of core and shell material like inorganic core/inorganic shell, inorganic core/organic shell, organic core/organic shell, and organic core/inorganic shell, or they are based on properties of core and shell, that is, core/multishell and a movable core/hollow shell core–shell nanomaterials. Out of all these classes, most important class of core–shell nanomaterials are inorganic core/inorganic shell core–shell materials. The core and shell are composed of silica, metal, metal oxide, or other inorganic compound. The inorganic core–shell materials further divides this category into two parts, that is, silica containing and nonsilica containing inorganic compound. Other subclasses of inorganic core/inorganic shell materials are semiconducting core–shell materials and lanthanides. Out of all these the semiconducting inorganic core/inorganic shell materials have been reported to have many applications in the field of photovolatics and will be given focus in this chapter.