Les processus photocatalytiques à la surface d’oxydes métalliques semi-conducteurs font l’objet d’intensesrecherches au niveau mondial car ils constituent des alternatives efficaces, respectueuses de l’environnement etpeu coûteuses aux méthodes conventionnelles dans les domaines de la purification de l’eau et de l’air, et de laproduction « verte » d’hydrogène. Cependant, certaines limitations pour atteindre des efficacitésphotocatalytiques élevées ont été mises en évidence avec les matériaux semiconducteurs classiques du fait de larecombinaison rapide des porteurs de charge générés par illumination. Le développement de photocatalyseurs àbase d’héterostuctures obtenues par dépôt de métaux à la surface de matériaux semiconducteurs ou parassociation de deux semiconducteurs possédant des bandes d’énergie bien positionnées devrait permettre delimiter ces phénomènes de recombinaison via un transfert de charge vectoriel. Dans ce contexte, trois typesd’hétérostructures telles que des nanomatériaux à base d’hétérojonction semiconducteur n/semiconducteur n(SnO2/ZnO), metal/semiconducteur n (RuO2/TiO2 and RuO2/ZnO) et semiconducteur p/semiconducteur n(NiO/TiO2) ont été synthétisées avec succès par différentes voies liquides. Leur composition, leur texture, leurstructure et leur morphologie ont été caractérisées par spectroscopies FTIR et Raman, par diffraction des rayonsX, microscopie électronique en transmission (MET) et porosimétrie de sorption d’azote. Par ailleurs, unecombinaison judicieuse des données issues de mesures effectuées par spectroscopie UV-visible en réflexiondiffuse (DRS) et par spectroscopies de photoélectrons X (XPS) et UV (UPS) a permis de déterminer lediagramme d’énergie des bandes pour chaque système étudié. Les catalyseurs ainsi obtenus ont conduit à desefficacités photocatalytiques plus élevées qu’avec le dioxyde de titane P25 pour la dégradation de colorantsorganiques (bleu de méthylène, l’orangé de méthyle) et la production d’hydrogène. En particulier, lesnanocomposites RuO2/TiO2 et NiO/TiO2 contenant une quantité optimale de RuO2 (5 % en masse) et de NiO(1% en masse), respectivement, ont conduit aux efficacités photocatalytiques les plus importantes pour laproduction d’hydrogène. Ces excellentes performances photocatalytiques ont été interprétées en termesd’alignement adéquat des bandes d’énergies des matériaux associé à des propriétés texturales et structuralesfavorables. Ce concept de photocatalyseurs à base d’hétérojonctions semiconductrices d’activité élevée devrait àl’avenir trouver des débouchés industriels dans les domaines de l’élimination de l’environnement de composésorganiques indésirables et de la production « verte » d’hydrogène. / Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV–visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

Photocatalytic processes over semiconducting oxide surfaces have attracted worldwide attention aspotentially efficient, environmentally friendly and low cost methods for water/air purification as well as forrenewable hydrogen production. However, some limitations to achieve high photocatalytic efficiencies havebeen found due to the fast recombination of the charge carriers. Development of heterostucture photocatalystsby depositing metals on the surface of semiconductors or by coupling two semiconductors with suitable bandedge position can reduce recombination phenomena by vectorial transfer of charge carriers. To draw newprospects in this domain, three different kinds of heterostructures such as n-type/n-type semiconductor(SnO2/ZnO), metal/n-type semiconductor (RuO2/TiO2 and RuO2/ZnO) and p-type/n-type semiconductor(NiO/TiO2) heterojunction nanomaterials were successfully prepared by solution process. Their composition,texture, structure and morphology were thoroughly characterized by FTIR, X-ray diffraction (XRD), Ramanspectroscopy, transmission electron microscopy (TEM) and N2 sorption measurements. On the other hand, asuitable combination of UV-visible diffuse reflectance spectroscopy (DRS), X-ray photoelectron spectroscopy(XPS) and ultraviolet photoemission spectroscopy (UPS) data provided the energy band diagram for eachsystem. The as-prepared heterojunction photocatalysts showed higher photocatalytic efficiency than P25 TiO2for the degradation of organic dyes (i.e. methylene blue and methyl orange) and the production of hydrogen.Particularly, heterostructure RuO2/TiO2 and NiO/TiO2 nanocomposites with optimum loading of RuO2 (5 wt %)and NiO (1 wt %), respectively, yielded the highest photocatalytic activities for the production of hydrogen.These enhanced performances were rationalized in terms of suitable band alignment as evidenced by XPS/UPSmeasurements along with their good textural and structural properties. This concept of semiconductingheterojunction nanocatalysts with high photocatlytic activity should find industrial application in the future toremove undesirable organics from the environment and to produce renewable hydrogen.

Among various nanomaterials, metal nanoparticles are the widely studied ones because of their pronounced distinct properties arising in the nanometer size regime, which can be tailored easily by tuning predominantly their size and shape. During the past few decades, scientists are engaged in developing new synthetic methodologies for the synthesis of metal nanoparticles which can be divided into two broad categories: i) top-down approach, utilizing physical methods and ii) bottom-up approach, employing chemical methods. As the chemical methods offer better control over particle size, numerous chemical methods have been developed to obtain metal nanoparticles with narrow size distribution. However, these two approaches have their own merits and demerits; they are not complementary to each other and also not sustainable for real time applications. Recent focus on the synthesis of metal nanoparticles is towards the development of green and sustainable synthetic methodologies. A solid state route is an exciting prospect in this direction because it eliminates usage of organic solvents thus, makes the overall process green and at the same time leads to the realization of large quantity of the materials, which is required for many applications. However, the major obstacle associated with the development of a solid state synthetic route is the lack of fundamental understanding regarding the formation mechanism of the nanoparticles in the solid state. Additionally, due to the heterogeneity present in the solid mixture, it is very difficult to ensure the proximity between the capping agent and nuclei which plays the most decisive role in the growth process. Recently, employment of amine–borane compounds as reducing agents emerged as a better prospect towards the development of sustainable synthetic routes for metal nanoparticles because they offer a variety of advantages over the traditional borohydrides. Being soluble in organic medium, amine– borane allows the reaction to be carried out in a single phase and due to its mild reducing ability a much better control over the nucleation and growth processes is realized. However, the most exciting feature of these compounds is that their reducing ability is not only limited to the solution state, they can also bring out the reduction of metal ions in the solid state. With the availability of a variety of amine–boranes of varying reducing ability, it opens up a possibility to modulate the nanostructure in both solid and solution states by a judicious choice of reducing agent. Although our current understanding regarding the growth behavior of nanoparticles has advanced remarkably, however, most often it is some classical model which is invoked to understand these processes. With the recent developments in in situ transmission electron microscopy techniques, it is now possible to unravel more complex growth trajectories of nanoparticles. These studies not only expand the scope of the present knowledge but also opens up possibilities for many future developments. Objectives • To develop an atom economy solid state synthetic methodology for the synthesis of metal nanoparticles employing amine–boranes as reducing agents. • To gain a mechanistic insight into the formation mechanisms of nanoparticles in the solid state by using amine–boranes with differing reducing ability. • Synthesis of bimetallic nanoparticles as well as supported metal nanoparticles in the solid state using ammonia borane as the reducing agent. • To develop a new in situ seeding growth methodology for the synthesis of core@shell nanoparticles composed of noble metals by employing a very weak reducing agent, trimethylamine borane and their transformation to their thermodynamically stable alloy counterparts. • Synthesis of highly monodisperse ultra-small colloidal calcium nanoparticles with different capping agents such as hexadecylamine, octadecylamine, poly(vinylpyrrolidone) and a combination of hexadecylamine/poly(vinylpyrrolidone) using the solvated metal atom dispersion (SMAD) method. To study the coalescence behavior of a pair of calcium nanoparticles under an electron beam by employing in situ TEM technique. Significant results An atom economy solid state synthetic route has been developed for the synthesis of metal nanoparticles from simple metal salts using amine–boranes as reducing agents. Amine–borane plays a dual role here: acts as a reducing agent thus brings out the reduction of metal ions and decomposes simultaneously to generate B-N based compounds which acts as a capping agent to stabilize the particles in the nanosize regime. This essentially minimizes the number of reagents used and hence simplifying and eliminating the purification procedures and thus, brings out an atom economy to the overall process. Additionally, as the reactions were carried out in the solid state, it eliminates use of organic solvents which have many adverse effects on the environment, thus makes the synthetic route, green. The particle size and the size distribution were tuned by employing amine–boranes with differing reducing abilities. Three different amine–boranes have been employed: ammonia borane (AB), dimethylamine borane (DMAB), and trimethylamine borane (TMAB) whose reducing ability varies as AB > DMAB >> TMAB. It was found that in case of AB, it is the polyborazylene or BNHx polymer whereas, in case of DMAB and TMAB, the complexing amines act as the stabilizing agents. Several controlled studies also showed that the rate of addition of metal salt to AB is the crucial step and has a profound effect on the particle size as well as the size distribution. It was also found that an optimum ratio of amine–borane to metal salt is important to realize the smallest possible size with narrowest size distribution. Whereas, use of AB and TMAB resulted in the smallest sized particles with best size distribution, usage of DMAB provided larger particles that are also polydisperse in nature. Based on several experiments along with available data, the formation mechanism of metal nanoparticles in the solid state has been proposed. Highly monodisperse Cu, Ag, Au, Pd, and Ir nanoparticles were realized using the solid state route described herein. The solid state route was extended to the synthesis of bimetallic nanoparticles as well as supported metal nanoparticles. Employment of metal nitrate as the metal precursor and ammonia borane as the reducing agent resulted in highly exothermic reaction. The heat evolved in this reaction was exploited successfully towards mixing of the constituent elements thus allowing the alloy formation to occur at much lower temperature (60 oC) compared to the traditional solid state metallurgical methods (temperature used in these cases are > 1000 oC). Synthesis of highly monodisperse 2-3 nm Cu/Au and 5-8 nm Cu/Ag nanoparticles were demonstrated herein. Alumina and silica supported Pt and Pd nanoparticles have also been prepared. Use of ammonia borane as the reducing agent in the solid state brought out the reduction of metal ions to metal nanoparticles and the simultaneous generation of BNHx polymer which encapsulates the metal (Pt and Pd) nanoparticles supported on support materials. Treatment of these materials with methanol resulted in the solvolysis of BNHx polymer and its complete removal to finally provide metal nanoparticles on the support materials. An in situ seeding growth methodology for the synthesis of bimetallic nanoparticles with core@shell architecture composed of noble metals has been developed using trimethylamine borane (TMAB) as the reducing agent. The key idea of this synthetic procedure is that, TMAB being a weak reducing agent is able to differentiate the smallest possible window of reduction potential and hence reduces the metal ions sequentially. A dramatic solvent effect was noted in the preparation of Ag nanoparticles: Ag nanoparticles were obtained at room temperature when dry THF was used as the solvent whereas, reflux condition was required to realize the same using wet THF as the solvent. However, no such behavior was noted in the preparation of Au and Pd nanoparticles wherein Au and Pd nanoparticles were obtained at room temperature and reflux conditions, respectively. This difference in reduction behavior was successfully exploited to synthesize Au@Ag, Ag@Au, and Ag@Pd nanoparticles. All these core@shell nanoparticles were further transformed to their alloy counterparts under very mild conditions reported to date. Highly monodisperse, ultrasmall, colloidal Ca nanoparticles with a size regime of 2-4 nm were synthesized using solvated metal atom dispersion (SMAD) method and digestive ripening technique. Hexadecylamine (HDA) was used as the stabilizing agent in this case. Employment of capping agent with a longer chain length, octadecylamine afforded even smaller sized particles. However, when poly(vinylpyrrolidone) (PVP), a branched chain polymer was used as the capping agent, agglomerated particles were realized together with small particles of 3-6 nm. Use of a combination of PVP and HDA resulted in spherical particles of 2-3 nm size with narrow size distribution. Growth of Ca nanoparticles via colaesence mechanism was observed under an electron beam. Employing in situ transmission electron microscopy technique, real time coalescence between a pair of Ca nanoparticles were detected and details of coalescence steps were analyzed.