Transition metal nanomaterials in catalysis Changlong Wang To cite this version: Changlong Wang. Transition metal nanomaterials in catalysis. Catalysis. Université Paul Sabatier - Toulouse III, 2017. English. NNT : 2017TOU30106. tel-01903837 HAL Id: tel-01903837 https://tel.archives-ouvertes.fr/tel-01903837 Submitted on 24 Oct 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. THÈSE En vue de l’obtention du DOCTORAT DE L'UNIVERSITÉ DE TOULOUSE Délivré par : Université Toulouse III Paul Sabatier (UT3 Paul Sabatier) Présentée et soutenue par : M. CHANGLONG WANG Vendredi 15 Septembre 2017 Nanomatériaux à base de métaux de transition pour la catalyse ED SDM : Chimie moléculaire - CO 046 Unité de recherche Laboratoire de Chimie de Coordination - CNRS - UPR 8241 Directeurs de thèse Lionel SALMON et Didier ASTRUC Membres du jury: M. Jean-Marie BASSET Professeur, Directeur du Centre de Catalyse, KAUST Rapporteur M. Jean-René HAMON Directeur de Recherche au CNRS, RENNES Rapporteur M. Christophe DERAEDT Chercheur à l'Université de Californie à Berkeley Examinateur Mme Montserrat GÓMEZ Professeur à l'Université Paul Sabatier Examinateur M. Azzedine BOUSSEKSOU Directeur CNRS, Directeur du LCC Membre invité M. Lionel SALMON Directeur de Recherche au CNRS Directeur de thèse M. Didier ASTRUC Professeur à l’Université de Bordeaux CoDirecteur de thèse Acknowledgement This thesis was completed in the Institute des Sciences Moléculaires (ISM), UMR CNRS N° 5255, University of Bordeaux and Laboratoire de Chimie de Coordination (LCC) UPR CNRS N° 8241, Université Toulouse III - Paul Sabatier. I would like to express my sincerest gratitude to my supervisors Prof. Didier Astruc and Dr. Lionel Salmon for their supports over the last four years, for supervising me and letting me take one more step towards my life long goal of becoming “a real scientist”. In particular, I am very grateful of having Prof. Didier Astruc as my thesis director for his inspiring, patient instruction, insightful criticism and expert guidance on my thesis. He has taught me, both consciously and un-consciously, how to be a good chemist. His profound knowledge of chemistry, consistent and illuminating instructions, and his contributions of time and ideas, making my Ph.D. experience productive and stimulating. I would like to warmly thank Dr. Azzedine Bousseksou, a prestigious scientist, for his precious administrative and scientific help that have greatly facilitated this thesis. I am also greatly indebted to the two reporters for the thesis, Professor Jean-Marie Basset from King Abdullah University of Science & Technology (KAUST), and Dr. Jean-René Hamon from the Université de Rennes I, and to the jury president Professor Montserrat Gómez from the Université Toulouse III - Paul Sabatier and to Dr. Christophe Deraedt from the University of California at Berkeley for their time and energy in serving as referees and examinators of the PhD and for helpful discussions. I am also deeply grateful to the engineer of our research group, Dr. Jaime Ruiz, for his patient guidance on experiment operations and helpful discussions. High tribute shall be paid to Sergio Moya, Danijela Gregurec, Joseba Irigoyen, Luis Yate and Jimena Tuninetti for their excellent collaborations and analyses on samples. My sincere gratitude also go to my former and current colleagues, including Yanlan Wang, Amalia Rapakousiou, Haibin Gu, Dong Wang, Na Li, Sylvain Gatard, Roberto Ciganda, Xiang Liu, Fangyu Fu and Qi Wang, who kindly gave me invaluable advises and help to solve various problems in both study and life. Last but not the least, my gratitude also extends to my family who have been assisting, supporting and caring for me all of my life. Special thanks should also go to all my friends who give me continuous support and encouragement during my thesis. Table of Content General Introduction………………………………………………...………………1 Chapter 1. Overview on Metal Catalyzed Alkyne–Azide Cycloaddition and Recent Trend……………………………………………………...………………….7 Chapter 2. An Amphiphilic Ligand for The Stabilization of Efficient Transition Metal Nanocatalysts in Aqueous Solution …………………………………….......29 2.1 Introduction……………………………………………...………….…………30 2.2 The design and applications of amphiphilic ligand for highly efficient transition metal nanoparticle catalysts in aqueous solutions...........................................32 2.3 From mono to tris-1,2,3-triazole-stabilized gold nanoparticles and their compared catalytic efficiency in 4-nitrophenol reduction…………..………122 2.4 Design and applications of an efficient amphiphilic “click” CuI catalyst in water…………………………………………………………...……………..152 Chapter 3. Efficient Heterogeneous Nanoparticles Catalysts Based on Graphene Supports………………………………………………………...………………….201 3.1 Introduction………………………………………………….……………….202 3.2 RhAg/rGO nanocatalyst: ligand-controlled synthesis and superior catalytic performances for the reduction of 4-nitrophenol…………...………………204 3.3 Efficient parts-per-million a-Fe2O3 nanocluster/graphene oxide catalyst for Suzuki–Miyaura coupling reactions and 4-nitrophenol reduction in aqueous solution……………………………………………………...………………239 3.4 Synthesis and high catalytic efficiency of transition-metal nanoparticle-graphene oxide nanocomposites……………..………………259 Chapter 4. Metal Organic Framworks Stabilize Efficient Non-noble Metal Nanoparticles Catalysis……………………………………...…………………….321 4.1 Introduction……… ……………………….………….…………...…………322 4.2 Hydrolysis of ammonia-borane over Ni/ZIF-8 nanocatalyst: high efficiency, ion effect and controlled hydrogen release. …………….……..…………………324 Conclusions and Perspective……………………………………………………...383 List of Published or Submitted Thesis Publications…………………………….387 General introduction Nanoscience and nanotechnology involve studying and working with matter on an ultrasmall scale and deal with the exploration, characterization and application of nanostructured materials. This area has undergone great prosperity and has become an emerging field of research for which significant studies have revolutionized the nanosystems.[1] Promises and possibilities are wide-ranging; for instance, nanomachines will transform modern medicine to the search for cancer cells or to deliver drugs.[2] Nanomaterials have stimulated great interest in optical, electrical, and mechanical applications, and among them nanocatalysts[3] have opened new routes for drug developments, clean energy conversion, environmental decontamination and green chemistry for fine chemical production. Homogeneous catalysts are usually solubilized in the reaction media and are very efficient, selective, and industrially useful, but they suffer from lack of recovery, reusability and limited thermal stability.[4] On the other hand, heterogeneous catalysts benefit from easy recovery from reaction media and possible use of high temperatures, but they suffer from selectivity problems and lack of mechanistic explorations. Furthermore, green catalysis,[5] that is critically addressed by the principles of green chemistry, is an important issue in modern chemical processes. Features of the green catalysts ideally involve low preparation costs, high activities, good selectivities, high stabilities, efficient recovery, and good recyclability. Green catalysts should efficiently catalyze reactions in “green” solvents (e.g., neat condition, water, ethanol). Finally the design and applications of green catalysts is not only a task of great economic and environmental importance in catalysis science, but also should overcome the problems of metal contamination in products. Nanocatalysis is defined by catalysis using nanoparticles (NP).[3] The catalytically active NPs have sizes between the order of one nanometer (nm) and several tens or hundreds of nanometers, but the most active ones in catalysis are only one or a few nanometers in diameter (containing a few tens to a few hundred atoms). They have a high surface-to-volume ratio and a large proportion of surface atoms, i.e. 1 predominantly edge and corner atoms that are very active for substrate activation. Since around the beginning of the 1990’s, this area of catalysis has become an independent field usually called colloidal catalysis or quasi-homogenous catalysis since it was believed, at that time, to be a bridge between classical homogenous catalysis and heterogeneous catalysis. In this regard, nanocatalysis combines the positive aspects of both homogenous catalysis (high catalytic activity and selectivity, and mechanistic studies leading to catalyst improvements) and heterogeneous catalysis (easy catalyst separation from reaction media and good recyclability).[4] In this context, transition metals based nanomaterials are of particular interest in the utilization of nanocatalysts.[6] Transition-metal-based heterogeneous nanomaterials contain the catalytic species that perform substrate activation, and the catalytic reaction proceeds on the supported metal surface thereby bringing about selectivity and efficiency. In order to obtain nano-sized catalytically active NPs, transition-metal