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Nanoparticles in Catalysis
Discover an essential overview of recent advances and trends in nanoparticle catalysis
Catalysis in the presence of metal nanoparticles is an important and rapidly developing research field at the frontier of homogeneous and heterogeneous catalysis. In Nanoparticles in Catalysis, accomplished chemists and authors Karine Philippot and Alain Roucoux deliver a comprehensive guide to the key aspects of nanoparticle catalysis, ranging from synthesis, activation methodology, characterization, and theoretical modeling, to application in important catalytic reactions, like hydrogen production and biomass conversion.
The book offers readers a review of modern and efficient tools for the synthesis of nanoparticles in solution or onto supports. It emphasizes the application of metal nanoparticles in important catalytic reactions and includes chapters on activation methodology and supported nanoclusters. Written by an international team of leading voices in the field, Nanoparticles in Catalysis is an indispensable resource for researchers and professionals in academia and industry alike.
Readers will also benefit from the inclusion of:
Perfect for catalytic, organic, inorganic, and physical chemists, Nanoparticles in Catalysis will also earn a place in the libraries of chemists working with organometallics and materials scientists seeking a one-stop resource with expert knowledge on the synthesis and characterization of nanoparticle catalysis.
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Veröffentlichungsjahr: 2021
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Table of Contents
Cover
Title Page
Copyright
Foreword
1 New Trends in the Design of Metal Nanoparticles and Derived Nanomaterials for Catalysis
1.1 Nanocatalysis: Position, Interests, and Perspectives
1.2 Metal Nanoparticles: What Is New?
1.3 Conclusions and Perspectives
References
2 Introduction to Dynamic Catalysis and the Interface Between Molecular and Heterogeneous Catalysts
2.1 Introduction
2.2 Dynamic Catalysis
2.3 Interface Between Molecular and Heterogeneous Catalysts
2.4 Summary and Conclusions
References
Part I: Nanoparticles in Solution
3 Metal Nanoparticles in Water: A Relevant Toolbox for Green Catalysis
3.1 Introduction
3.2 Protection by Ligands
3.3 Stabilization by Surfactants
3.4 Stabilization by Polymers
3.5 Conclusions and Perspectives
References
4 Organometallic Metal Nanoparticles for Catalysis
4.1 Introduction
4.2 Interests of the Organometallic Approach to Study Stabilizer Effect on Metal Surface Properties
4.3 Application of Organometallic Nanoparticles as Catalysts for Hydrogenation Reactions
4.4 Conclusions
References
5 Metal Nanoparticles in Polyols: Bottom‐up and Top‐down Syntheses and Catalytic Applications
5.1 Introduction
5.2 Bottom‐up Approach: Colloidal Synthesis in Polyols
5.3 Top‐down Approach: Sputtering in Polyols
5.4 Summary and Conclusions
Acknowledgments
References
6 Catalytic Properties of Metal Nanoparticles Confined in Ionic Liquids
6.1 Introduction
6.2 Stabilization of Metal Nanoparticles in ILs
6.3 Synthesis of Soluble Metal Nanoparticles in ILs
6.4 Catalytic Application of NPs in ILs
6.5 Conclusions
Acknowledgments
References
Part II: Supported Nanoparticles
7 Nanocellulose in Catalysis: A Renewable Support Toward Enhanced Nanocatalysis
7.1 Introduction
7.2 Nanocellulose‐Based Catalyst Design and Synthesis
7.3 Organic Transformations Catalyzed by Metal NP/nanocellulose Hybrids
7.4 Conclusions
References
8 Magnetically Recoverable Nanoparticle Catalysts
8.1 Introduction
8.2 Magnetic Support Material
8.3 Preparation of Magnetically Recoverable Metal Nanoparticle Catalysts
8.4 Summary and Conclusions
References
9 Synthesis of MOF‐Supported Nanoparticles and Their Interest in Catalysis
9.1 Introduction
9.2 General Synthetic Methodologies
9.3 Architectural Designs and Catalytic Applications of MNP/MOF Nanocomposites
9.4 Summary and Conclusions
References
10 Silica‐Supported Nanoparticles as Heterogeneous Catalysts
10.1 Introduction
10.2 Deposition Methods of Metal NPs
10.3 Application of Silica‐Supported NPs in Catalysis
10.4 Conclusion
References
Part III: Application
11 CO
2
Hydrogenation to Oxygenated Chemicals Over Supported Nanoparticle Catalysts: Opportunities and Challenges
11.1 Introduction
11.2 CO
2
Hydrogenation into Formic Acid
11.3 CO2 Hydrogenation to Methanol
11.4 CO2 Hydrogenation to Dimethyl Ether
11.5 Perspectives and Conclusion
Acknowledgment
References
12 Rebirth of Ruthenium‐Based Nanomaterials for the Hydrogen Evolution Reaction
12.1 Introduction
12.2 Relevant Figures of Merit
12.3 Factors Ruling the Performance of Ru‐Based NPs in HER Electrocatalysis
12.4 Factors Ruling the Performance of Ru‐Based NPs in HER Photocatalysis
12.5 Summary and Conclusions
Acknowledgments
References
13 Nanocatalytic Architecture for the Selective Dehydrogenation of Formic Acid
13.1 Introduction
13.2 Monometallic Palladium‐Based Nanocatalysts
13.3 Bimetallic Palladium‐Based Nanocatalysts
13.4 Summary and Conclusions
Acknowledgments
References
Part IV: Activation and Theory
14 Magnetically Induced Nanocatalysis for Intermittent Energy Storage: Review of the Current Status and Prospects
14.1 Introduction
14.2 General Context and Historical Aspects
14.3 Characteristics of the Nanocatalysts Used in Magnetic Hyperthermia
14.4 Catalytic Applications in Liquid Solution and Gas Phase
14.5 Perspectives
14.6 Perspective of the Integration for Renewable Energy Use
14.7 Conclusion
References
15 Sabatier Principle and Surface Properties of Small Ruthenium Nanoparticles and Clusters: Case Studies
15.1 Introduction
15.2 C–H Activation and H/D Isotopic Exchange in Amino Acids and Derivatives
15.3 Hydrogen Evolution Reaction
15.4 Summary
15.5 Computational Details
Acknowledgments
References
Index
End User License Agreement
List of Tables
Chapter 3
Table 3.1 Overview of recent catalytic applications with ligand‐stabilized me...
Table 3.2 Overview of recent catalytic applications with polymer‐stabilized m...
Chapter 4
Table 4.1 Enantioselective hydrogenation of prochiral ketones catalyzed by Ir...
Table 4.2 Cinnamaldehyde hydrogenation with bimetallic NPs Ru
1
Pt
1
, Ru
1
Pt
2
, an...
Table 4.3 Catalytic hydrogenation of propargylamines with the magnetic Pd nan...
Table 4.4 Hydrogenation of furfural catalyzed by carbon‐supported Pd NP under...
Chapter 6
Table 6.1 Examples of catalytic hydrogenation of aromatic compounds in ILs us...
Chapter 10
Table 10.1 Different types of silica and their characteristics.
Table 10.2 Catalytic hydrogenation of various aromatic nitro compounds over A...
Table 10.3 Comparison of DFNS‐PEI/Pd with other catalysts for the carbonylati...
Chapter 11
Table 11.1 Reaction conditions and catalytic performance of various metal NP‐...
Chapter 13
Table 13.1 The catalytic activity comparison of Pd‐based bimetallic alloy and...
Table 13.2 The catalytic activity comparison of Pd‐based trimetallic nanocata...
Chapter 14
Table 14.1 Main features of selected magnetic nanoparticles that are adapted ...
Table 14.2 Heterogeneous catalysis achieved by magnetic heating of nanocataly...
Table 14.3 Selected chemical reactions in solution activated by magnetic hype...
List of Illustrations
Chapter 1
Figure 1.1 Schematic overview of the main but not exhaustive trends currentl...
Chapter 2
Figure 2.1 (a) Pathways of palladium particle conversion in a catalytic syst...
Figure 2.2 Palladium metal nanoparticles catalyze (a) C–C cross‐couplings,...
Figure 2.3 (a–c) SEM images of reaction mixtures for various CS bond format...
Figure 2.4 Negative ion mode electrospray ionization mass spectra of [Pd
2
dba
Figure 2.5 Facets of Pd nanoparticles representing (1 1 1) and (1 0 0) surfa...
Figure 2.6 Schematic representation of the model pathways of Pd atom detachm...
Scheme 2.1 Operating principle of the mercury test in the mechanistic studie...
Scheme 2.2 Selected examples of reactions of (a) M
0
and (b) M
II
complexes wi...
Scheme 2.3 Principal examples of poisoning in dynamic systems. (a) Homogeneo...
Chapter 3
Figure 3.1 1,3,5‐Triaza‐7‐phosphaadamantane‐protected ruthenium and platinum...
Figure 3.2 Diphosphine‐coated Ru NPs. Comparison in styrene hydrogenation....
Figure 3.3 Hydrogenation of polyunsaturated methyl esters of soybean oil wit...
Figure 3.4 Water‐soluble Pd NPs stabilized with sulfonated NHC ligands as re...
Figure 3.5 Comparison of sulfonated NHC‐stabilized Pd NPs prepared by variou...
Figure 3.6 Water‐soluble Pd NPs for Suzuki–Miyaura coupling reaction.
Figure 3.7
N
‐(Hydroxyalkyl)‐
N
‐alkylammonium salts as efficient bilayer prote...
Figure 3.8 Optimization of the surfactant features in the reduction of aniso...
Figure 3.9 Turnover catalytic activities (TOF h
−1
values) in the reduc...
Figure 3.10 Optically active aqueous suspensions of metal nanoparticles – To...
Figure 3.11 Ammonium surfactant‐stabilized Ru NPs for oxidation of α‐pinene
Figure 3.12 Surfactant‐stabilized metal nanoparticles in other catalytic app...
Figure 3.13 PVP and carboxylate‐modified PVP‐coated Rh NPs for arene hydroge...
Figure 3.14 Influence of various phosphines on PVP‐coated Rh NPs on the chem...
Figure 3.15 PVA‐protected palladium colloids for the selective hydrogenation...
Figure 3.16 P123‐protected ruthenium(0) NPs for the reduction of α‐pinene in...
Figure 3.17 M6PEI/HEA16Cl self‐assembly‐stabilized Pd(0) colloids. Correlati...
Figure 3.18 Glycodendrimer‐stabilized Pt nanoparticles as a catalyst for hyd...
Figure 3.19 Cucurbit[6]uril‐coated Pd NPs for hydrogenations.
Figure 3.20 PEG@Pd NPs, efficient catalyst for carbon–carbon couplings.
Figure 3.21 PEG‐tagged capping agent of Pd NPs for Suzuki couplings.
Figure 3.22 PVP‐protected Pd NPs for Tsuji–Trost allylations.
Figure 3.23 G
3
DenP‐capped Ni NPs for Stille coupling reactions.
Figure 3.24 Pd@CB‐PN‐catalyzed C–C and C–N bond forming reactions.
Figure 3.25 Comparison of various bi‐ or trimetallic alloys on the glucose o...
Chapter 4
Figure 4.1 Organometallic approach for the synthesis of metal nanoparticles....
Figure 4.2 Schematic view of some surface studies performed on ruthenium nan...
Figure 4.3 N‐heterocyclic carbenes used as ligands to stabilize metal nanopa...
Figure 4.4 Zwitterionic imidazolium‐amidinate (betaine) ligands.
Figure 4.5 (a) TEM micrograph of Ru/C
60
1/1. (b) STEM of Ru/C
60
1/1 (scale b...
Figure 4.6 (a–d) Electron tomography analysis of a representative aggregate ...
Figure 4.7 TEM (top) and HRTEM (bottom) images of Ni NP: (a) Ni‐HDA, (b) Ni‐...
Chapter 5
Scheme 5.1 Stepwise oxidation of ethylene glycol to CO
2
.
Figure 5.1 Schematic illustration of AgNP core (macro)molecule shell. The me...
Scheme 5.2 Heck cross‐coupling reactions of aryl halides and alkenes catalyz...
Figure 5.2 Schematic representation of the overall redox mechanism for the s...
Figure 5.3 TEM images of PdNPs in neat glycerol stabilized by different liga...
Figure 5.4 (A) Synthesis of Cu(0) nanoparticles
CuX
(X denotes the copper pr...
Figure 5.5 (A) PdCu NPs (
Pd1Cu1
) prepared by coreduction of metal precursors...
Figure 5.6 Schematic representation of the synthesis of carbohydrate‐thiosem...
Figure 5.7 (A) Synthesis of PtNPs using the polyphenol BWT as amphiphilic st...
Figure 5.8 TEM micrographs of FePd NPs at different magnifications (a) 100 n...
Scheme 5.3 (a) [3+2] Cycloadditions of 1,4‐naphthoquinones with β‐ketoamides...
Figure 5.9 Scheme of the sputtering vacuum chamber used for the synthesis of...
Figure 5.10 TEM images of PtNPs (a) and PtNi bimetallic nanoparticles (b) on...
Chapter 6
Figure 6.1 3‐D structural arrangement representations of an ionic crystal di...
Scheme 6.1 Schematic representation of the preparation of metal NPs in ILs b...
Figure 6.2 Structure and abbreviations of ILs discussed in this chapter.
Figure 6.3 Mechanistic representation of catalytic benzene hydrogenation. S ...
Scheme 6.2 Possible pathways involved in the Heck reaction promoted by Pd NP...
Scheme 6.3 CO
2
hydrogenation to the higher hydrocarbons driven by Ru/Ni NPs ...
Chapter 7
Scheme 7.1 Nano (left) and chemical structure (right) of CNCs produced from ...
Figure 7.1 Number of publications per year on the topic of cellulose nanocry...
Figure 7.2 Schematic view of the use of CNC‐based catalysts for the conversi...
Figure 7.3 Schematic view of the pulsed synthesis method for the generation ...
Figure 7.4 Scanning electron microscopy (SEM) images of carboxymethylated CN...
Figure 7.5 Comparative schematic illustration of the preparation of graphiti...
Scheme 7.2 Examples of C–C coupling reactions catalyzed by nanocellulose‐sup...
Scheme 7.3 Reduction reactions catalyzed by nanocellulose‐supported nanocata...
Chapter 8
Figure 8.1 Principle of magnetic separation of a catalyst by simple applicat...
Figure 8.2 Strategies for magnetically recoverable catalysts: (a) deposition...
Figure 8.3 Silica‐coated magnetic nanoparticles prepared by different method...
Figure 8.4 Silica‐coated magnetic nanoparticles prepared by reverse microemu...
Figure 8.5 Ligand‐assisted preparation of supported metal NP catalysts.
Figure 8.6 TEM micrographs of (a) Pt NPs () (b) Rh NPs ((c) Au NPs (...
Figure 8.7 TEM micrographs of Pd NPs.
Figure 8.8 Ligand‐assisted activation of supported Au NPs in hydrogenation r...
Figure 8.9 Impact of the addition of ethylenediamine on Pd NP activity.
Chapter 9
Figure 9.1 Schematic illustration showing the spatial locations of MNPs in t...
Figure 9.2 Schematic illustration of the modification of Zr‐fcu‐MOFs through...
Figure 9.3 (a) Schematic illustration of the transformation of Cu
2
O nanocube...
Figure 9.4 (a,b) TEM image of Au/MIL‐101 prepared by colloidal deposition me...
Figure 9.5 Schematic illustration showing the synthetic strategies of MNP/MO...
Figure 9.6 (a–c) Topology and hexagonal/pentagonal windows in the MIL‐101(Fe...
Figure 9.7 Schematic illustration of immobilization of the AuNi alloy NPs on...
Figure 9.8 Schematic illustration of one‐pot synthesis of Pt@DUT‐5.
Figure 9.9 (a,b) Representative TEM images of the wire‐like MOF‐545, (c) rep...
Figure 9.10 (a) Schematic illustration of preparations of bulk MOF, 2D MOF n...
Figure 9.11 (a–c) Schematic illustration of three types of spatial configura...
Figure 9.12 (a) Schematic illustration of preparation of MIL‐101@Pt@MIL‐101 ...
Figure 9.13 Schematic illustration of the synthesis of the Au@ZIF‐8 nanoreac...
Chapter 10
Figure 10.1 TEM images of (a) 0.2 wt% Pt/SBA‐15 and (b), (c) 0.2 wt% Pt/SBA‐...
Figure 10.2 TEM images of Pt/SBA‐15 prepared by the deposition–precipitation...
Figure 10.3 Metal NP encapsulation using dendrimeric approach, followed by l...
Figure 10.4 TEM images for the samples of (a) 0.5PtAS, (b) 1.0PtAS, (c) 3.0P...
Figure 10.5 TEM images of Pt/SBA‐15 prepared by postsynthetic grafting metho...
Figure 10.6
High‐resolution transmission electron microscopy
(
HRTEM
) b...
Figure 10.7 Performance of various Pd–Au composition catalysts for benzyl al...
Figure 10.8 Mechanism of dimethylphenylsilane oxidation using Au NPs.
Figure 10.9 Preparation of dendrimer‐functionalized SBA‐15 and supported Pd ...
Figure 10.10 Plasmonic effect of Ag deposited onto CeO
2
coated with silica (...
Figure 10.11 Synthesis of DFNS‐NH
2
/Pd nanocatalysts.
Figure 10.12 Pd NPs immobilized on Schiff base‐functionalized mesoporous sil...
Figure 10.13 Synthetic route to the ASNTs@Pd composite.
Figure 10.14
Scanning electron microscopy
(
SEM
) and TEM of ASNT support and ...
Chapter 11
Figure 11.1 Schematic representation of CO
2
‐mediated H
2
energy cycle.
Figure 11.2 Comparison of the catalytic activities of various supported Pd–A...
Figure 11.3 Reaction equations of CO
2
hydrogenation and the formation of met...
Figure 11.4 Schematic illustration of the CO
2
hydrogenation into DME via a b...
Chapter 12
Figure 12.1 Schematic representation of the HER pathways on nanoparticulate ...
Figure 12.2 Schematic representation of the organometallic method for the sy...
Figure 12.3 Schematic representation of the conversion processes between the...
Figure 12.4 DFT calculated σ and π coordination modes (and corresponding ads...
Figure 12.5 Schematic representation of the synthesis of the hierarchically ...
Figure 12.6 Schematic representation of the synthesis of the hierarchically ...
Figure 12.7 Schematic representation of the synthesis of the Ru
2
P@PNC/CC‐900...
Figure 12.8 Schematic representation of the
η
10
(white bars) and the Ta...
Chapter 13
Scheme 13.1 Carbon‐neutral fuel cycle diagram.
Scheme 13.2 Proposed FA dehydrogenation pathways.
Figure 13.1 (a) Schematic illustration for the fabrication of Pd/PDA‐rGO, (b...
Scheme 13.3 Schematic illustration for the synthesis of Pd/MSC‐30 and Pd/N‐M...
Scheme 13.4 Different forms of Pd‐containing bimetallic catalysts: (a) physi...
Scheme 13.5 Schematic illustration of AgPd/MOF‐5‐C‐900 preparation for catal...
Scheme 13.6 Possible reaction pathway for the dehydrogenation of FA over PdA...
Figure 13.2 Atom map (a) of an individual Ag@Pd nanoparticle, clearly showin...
Scheme 13.7 Schematic illustration for the preparation of Au@Pd/N‐rGO nanoca...
Scheme 13.8 (a) The schematic illustration of the synthesis protocol followe...
Figure 13.3 HRTEM images of (a) Pd
0.60
Co
0.18
Ni
0.22
/TiO
2
–ALD–SiO
2
(6‐cycles),...
Scheme 13.9 Schematic illustration of the synthesis for KCC‐1/IL/PbS nanopar...
Chapter 14
Scheme 14.1 Hydrodeoxygenation (HDO) reactions catalyzed in solution in the ...
Figure 14.1 Potential use of magnetic heating for low carbon footprint use o...
Figure 14.2 Catalysis using magnetic heating integration into a life cycle a...
Chapter 15
Figure 15.1 Schematized H (white atoms) /D (light gray atoms) substitution a...
Figure 15.2 Adsorbed isopropylamine model before (
1
N*,CH
) and after (
1
N*
...
Figure 15.3 Simplified H/D exchange mechanism plotted as energy profiles. Da...
Figure 15.4 Energy diagram for the Langmuir–Hinshelwood‐type H/D exchange me...
Figure 15.5 DOS of the [(CH
3
)
2
CHNH
2
] *Ru
13
D
x
compound. Long dashes: DOS proj...
Figure 15.6 Volcano‐like behavior of the experimental exchange current densi...
Figure 15.7 Probed adsorption sites (a–f) for HER on a 4PP‐protected 1 nm Ru...
Figure 15.8 (a)
d
‐Band center and pMPA charges of surface metal atoms in Ru
5
...
Figure 15.9 Ru
13
H
14
L
x
clusters,with L
x
= (CO)
6
, (CO)
12
, (MeCOO)
3
, (MeCOO)
6
, ...
Figure 15.10 Evaluation of the possible HER activity of various Ru
13
H
14
L
n
cl...
Guide
Cover
Table of Contents
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Nanoparticles in Catalysis
Advances in Synthesis and Applications
Edited byKarine PhilippotAlain Roucoux
Editors
Dr. Karine Philippot
Laboratoire de Chimie de Coordination
du CNRS UPR 8241
205, route de Narbonne
BP44099
31077 Toulouse Cedex 04
France
Prof. Alain Roucoux
ENS Chimie de Rennes
UMR CNRS 6226
11, allée de Beaulieu
CS 50837
35708 Rennes Cedex 7
France
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Library of Congress Card No.:
applied for
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Foreword
In the recent decades, nanosciences and nanotechnologies have revolutionized the approaches of the researchers and the view of the public, and nanocatalysis stands as one of their most prominent aspects. Catalysis is involved in a majority of biological processes as well as in the transformation of chemicals and energy sources indispensable in today society.
A number of crucial industrial catalytic processes discovered in the beginning of the twentieth century have allowed the transformation of raw materials into fine chemicals using heterogeneous catalysts, whereas homogeneous catalysis involving a good control of kinetics, mechanisms, and consequently of high selectivities was only developed in the last quarter of the twentieth century. Neither heterogeneous nor homogeneously catalysis has produced perfect catalysts with the key desired properties of efficiency, selectivity, recyclability, and green chemistry like those encountered in enzymes. It is the merging of these two communities of catalysis that is at the origin of the of bottom‐up concept of nanosized catalysts bringing a molecular dimension to heterogeneous catalysis.
Perhaps the understanding of the advantage of conducting catalysis with the smallest particle was realized by Paul Sabatier more than hundred years ago. Nanocatalysis itself was seldom addressed before the 1980's, however, when instruments such as the scanning tunneling microscope permitting the adequate characterization of nanoparticles were invented and later also applied to the fabrication of useful nanomaterials.
Our modern Society urgently requires meeting the fundamental needs involving sustainable development, clean energy, and advanced medicine, all calling for novel catalytic tools with which synergies, optimized nanocatalysts, and designed interfaces between nanoparticles and supports must be developed.
An immense body of research advances in nanocatalysis has already been achieved in the past 40 years and particularly since the 2000's. Therefore, this new book “Nanoparticles in Catalysis: Advances in Synthesis and Applications,” edited by Dr. Karine Philippot (LCC, Toulouse) and Professor Alain Roucoux (ENSCR, Rennes), distinguished by their high standing and in particular their reputation in the field defined by the book title, is timely and most welcome. The editors have themselves authored a useful introductory chapter showing the new trends in the design of metal nanoparticles and derived nanomaterials for catalysis. They have also gathered among the best experts who have authored 15 excellent book chapters.
Altogether, this book, judiciously divided into four parts: nanoparticles in solution, supported nanoparticles, application, and activation and theory, covers the whole area of modern nanocatalysis and lays the foundation for further research challenges, developments, and applications.
Bordeaux, April 2020
Didier Astruc
1New Trends in the Design of Metal Nanoparticles and Derived Nanomaterials for Catalysis
Alain Roucoux1and Karine Philippot2
1Université de Toulouse, UPS, INPT, CNRS, LCC (Laboratoire de Chimie de Coordination), UPR 8241, Toulouse Cedex 4, F‐31077, France
2Univ Rennes, Ecole Nationale Supérieure de Chimie de Rennes, CNRS, ISCR – UMR 6226, 11, allée de Beaulieu, Rennes, F‐35000, France
1.1 Nanocatalysis: Position, Interests, and Perspectives
Being part of heterogeneous catalysts, metal nanoparticles (NPs) have been known for a long time (see for instance the pioneering works of P. Sabatier [1] and L.D. Rampino and F.F. Nord [2]), but a renewed interest has emerged in the past three decades for the design of better‐defined systems [3]. Interestingly, a great part of the former heterogeneous catalysis community is now merging into the nanoparticle one [4]. Thus, as it can be observed in the literature through the overincreasing number of papers and patents published by both academic and industrial institutes, huge research efforts are devoted to the synthesis of more precisely defined metal nanospecies and even more recently at an atomic precision level [5–7], as well as the study of their characteristics. This keen interest for nanoscale metal‐based species derives from their particular matter state (finely divided metals) and their electronic parameters, thus influencing the physical and chemical properties that these entities possess in comparison with bulk metals and molecular complexes. Small nanoparticles are usually called nanoclusters, but there is a continuum of situations from molecules to solid state between small clusters defined by molecular orbitals and larger nanoparticles defined by energy band structures. These various types differ by the number of metal atoms, the nature of the stabilizing ligands, and the dispersity. Rigorously, the term cluster or nanocluster only concerns molecularly polymetallic assemblies with ligands for which the X‐ray crystal structure is known, whereas the term nanoparticles is used for mixtures of more or less polydisperse large nanoclusters defined by the histogram disclosed by transmission electron microscopy (TEM) measurement [4]. Besides the fundamental aspects of the research around metal nanoparticles, the interest is also governed by the potential applications that they may find. The unique properties of nanosized metal particles make them very attractive materials for various domains of applications including optoelectronics, sensing, biomedicine, energy conversion, storage, and catalysis, as nonexhaustive examples [8–11]. Concerning this last field, several books dedicated to nanocatalysis have been edited in the past 15 years [1, 12]. Indeed, metal nanoparticles are particularly interesting catalytic species because of the high surface‐to‐volume ratio they display. This ratio is promising when metal nanoparticles are at a size as close as 1 nm, or even below (subnanoparticles), because the number of surface atoms can be >90%, thus providing a great number of potential active sites. Remarkably, the subnanometric particles of late transition metals have been reported as very active, although the optimum catalytic activity is believed to be attained with particles containing between 12 and 20 atoms (i.e. sizes close to 1 nm or slightly below) [13]. The atomic sites exposed in metal nanoparticles may have various reactivities owing to their different coordination numbers according to their situation on the surface (corner, edge, and face atoms). By the way, the development of synthesis tools that enable to produce ultrasmall nanoparticles remains of prime importance in order to promote high surface area combined with an efficient distribution of surface atoms. Indeed, the proportion of edge and corner surface atoms possessing lower coordination numbers increases with the decrease in the particle size. Besides the size, other key morphological parameters need to be controlled. Thus, the crystalline structure is also of great importance because according to the types of crystalline plans that can be exposed at the surface, different catalytic properties could be achieved. Controlling the particles shape also constitutes another route to orientate the crystalline plans exposed [14–16]. The last but not the least key parameter is the composition of the metal nanoparticles that has to be adjusted depending on the targeted catalytic reaction. Apart from the nature of the metallic core that may govern the reactivity (some metals are well known for certain catalytic applications but not for others), the surrounding stabilizer for colloidal catalysis (ionic liquids [ILs], polymers, dendrimers, surfactants, polyols, ligands, etc.) or the support for supported catalysis (metal oxides such as silica, metal organic frameworks [MOFs], carbon derivatives, nanocelluloses, etc.) may also influence or even orientate the catalytic performances. While calcination is typically applied in traditional heterogeneous catalysis in order to suppress any organics and liberate the active sites, such treatment on small nanoparticles can be critical, thus potentially leading to their sintering. Moreover, naked nanospecies are not always optimal catalysts. In modern nanocatalysis, the presence of organic ligands onto the particle surface is not considered as detrimental for catalytic applications but could be a way to improve or even modify the chemoselectivity [17]. Aiming at catalysis by appropriate design, current developments in nanochemistry dedicated to catalytic applications often rely with multifunctionality [18]. This can be achieved by the proper design of nanohybrids, the term hybrid referring to the appropriate association between a metal core and a stabilizing shell or a support. When using typical ligands from coordination chemistry as capping agents, a parallel can be performed with molecular catalysis. Indeed, the interaction of the ligands with the metal atoms on the particle surface can be compared to ligand interactions with the metal centers in homogeneous complexes and is a parameter of paramount importance for stability and catalytic performances (activity and selectivity properties). Thus, ligands can be chosen in order to tune the surface properties of metal nanoparticles through steric and/or electronic effects [19, 20]. The challenge remains to find protective agents that are able to stabilize well‐defined nanoparticles while controlling accessibility at the metal surface and reactivity [13, 21]. Strongly bound capping ligands (such as thiols or phosphines) can result in the poisoning of a nanocatalyst at high surface coverage. However, the presence of a limited amount of ligand can be beneficial in terms of catalytic performances (suitable and replicable activities and/or selectivities). The strong coordination of a ligand at a metal surface can also be a way to block selectively some active sites in order to orientate the catalysis evolution. In comparison with the investigation of facet dependency [12, 22], the ligand influence on the catalytic activity has been less intensively studied, but recent results well illustrate the interest to do so [23–27]. Capping agent‐stabilized metal nanoparticles can be applied to catalysis as stable colloidal suspensions in various media (water, polyols, and organic solvents) but also in heterogeneous conditions after their deposition on the surface or confinement in the pores of solid supports [28]. Ionic liquids [29] are also very efficient to stabilize metal nanoparticles, and their colloidal suspensions can even be deposited onto inorganic materials [30]. When employing a support, it not only prevents nanoparticle aggregation but may also act in synergy with nanoparticle surface and favor the activation of substrates in a manner comparable to the positive synergy observed between two transition metal atoms in alloys or between a transition metal and a main group element such as nitrogen. Therefore, it was found that N‐doped carbon supports were superior to undoped analogs because of such synergy effects [4].
Thus, having in hand synthesis strategies that allow access, in a reproducible manner, to well‐defined metal nanoparticles in terms of size, crystalline structure, composition (metal cores and stabilizing agents), chemical order (bimetallic or ternary systems), shape, and dispersion constitutes a beneficial condition to finely investigate the catalytic properties of metal nanoparticles and define structure/properties relationships. Taking advantage of recent developments in nanochemistry that offer efficient tools to reach these objectives, nanocatalysis is now well established as a borderline domain between homogeneous and heterogeneous catalysis. With a molecular approach, nanocatalysts can be considered as assemblies of individual active sites where metal–metal bonds will also have influence [31]. Precisely designed nanohybrids (including the choice of an adequate and noninnocent stabilizer or support) are expected to present benefits from both homogeneous and heterogeneous catalysts, namely, high reactivity and better selectivity [32]. One aim lies in the design of more performant nanocatalysts in order to develop more efficient and eco‐compatible chemical production [33]. If huge progress has been performed in the past decade, this topic still remains challenging, in particular with the crucial need to develop multigram‐scalable catalytic routes presenting a reduced environmental footprint and economically viable cost for industrial applications. Furthermore, model catalysts are also needed in order to better understand the relationship between the characteristics of metal nanoparticles and their catalytic performances and thus bridge the gap between model surfaces and real catalysts. Each progress that contributes to reduce the gap of knowledge between nanocatalysts and homogeneous catalysts constitutes a step forward the development of more efficient catalytic systems. Efforts have thus to be pursued in order to one day be able to anticipate the design of suitable catalysts for a given reaction.
Various metals are investigated in nanocatalysis toward these principles, with a huge number of studies dedicated to gold, which is highly reputed for CO oxidation and emerges now in hydrogenation catalysis [34, 35] or palladium as a relevant metal for various C–C coupling reactions and also catalytic hydrogenation [36, 37]. Other metals such as rhodium, ruthenium, platinum, iridium, nickel, cobalt, and iron among others are also the subject of numerous studies. Some of these metals, generally called earth abundant, such as iron and cobalt or more recently manganese or copper have attracted increasing attention in the field of nanocatalysis because of their low cost, ready availability, low toxicity, and greater sustainability [38, 39]. Indeed, for many traditional catalytic transformations and challenging reactions, earth‐abundant transition metal nanoparticle catalysts have already appeared as attractive alternatives to noble ones.
Figure 1.1 Schematic overview of the main but not exhaustive trends currently developed in the area of nanocatalysis and illustrated through the chapters contents of this book.
The purpose of this book is to provide the readers a synthetic overview of the recent advances in research that address the investigation of well‐controlled metal nanoparticles in the domain of catalysis in suspension conditions (colloidal catalysis) and supported conditions.
1.2 Metal Nanoparticles: What Is New?
As mentioned above, nanocatalysis, being an exciting research area at the frontier between homogeneous and heterogeneous fields, has known a huge evolution during the past 25 years. This great interest mainly derives from the original catalytic properties that nanoparticles offer but also to the great advances in their synthesis in solution (aqueous, organic, glycerol, polyols, or ionic liquids, as main examples) or onto supports. Also, the combination of complementary analytical techniques from both molecular chemistry and solid chemistry together with the development of computational chemistry tools for the study of their surface state and/or modeling accounts for this still growing interest. Worldwide, numerous scientists are involved in both “nanochemistry” and “nanocatalysis” with a main and common objective, the design of well‐controlled nanoparticles in terms of size, dispersion, and surrounding environment to afford high and/or original catalytic performances.
Compared to previous methodologies in which metal nanoparticles were produced almost exclusively via heterogeneous approaches (top‐down approach), current strategies offer a better control of the nanoparticle characteristics (bottom‐up approach). Nanometer‐sized transition metal particles for catalysis, usually called “nanocatalysts,” are structure sensitive; their properties in terms of activities and selectivities depend on their core‐size, shape, morphologies as well as nature, composition, and their support materials. Nanocatalysis includes the development of metallic and metal oxide nanoscale materials with defined structure and morphology, and their use as active species or as supports of the active phase.
This book will provide the readers a basic knowledge on the current trends in the domain of metal nanoparticle engineering and of derived composite materials, all the research efforts were devoted to reach not only better catalytic performances but also a better understanding of the key parameters in nanocatalysis. A large range of data from the synthesis of metal nanoparticles, either in solution or deposited onto various supports, to their application as nanocatalysts in diverse catalytic reactions have been collected. Actually, each chapter of this book proposes a critical overview on the concerned subject through the discussion of relevant examples from the recent literature.
The 15 chapters of this book cover a wide range of subfields by exploring in detail a great variety of nanocatalysts, catalytic media, catalytic reactions, and potentially their external activation. Following two introductive chapters dedicated to general interests of metal nanoparticles (Chapter 1) and their position between molecular and heterogeneous catalysts (Chapter 2), four thematic ensembles of chapters structure this book (Figure 1.1). The first two sets concern nanoparticles as active species in solution (Set I) or deposited onto supports (Set II). Set III is devoted to sustainable applications for energy production or upgrading of renewables. In Set IV, recent advances in physical activation of nanocatalysts for avoiding classical heating are first illustrated. Then, examples on the contribution of computational chemistry dedicated to metal nanostructures are discussed. This subdomain provides theoretical insights and modelings of nanocatalysts for a better understanding of the metal surface environment and of catalytic reactions that occur there.
Chapter 2 constitutes a strategic introduction on the nature of nanoparticle‐based catalysts at the interface between molecular complexes and heterogeneous systems. Based on experimental results issued from several analytical techniques such as electron microscopy, mass spectrometry, mercury tests, etc., this chapter reports on the difficulties to reveal the true nature of the active species in dynamic catalysis. According to the catalytic applications, nanoparticles, nanoclusters, mononuclear complexes, and multicenter metal complexes can be simultaneously present, providing cocktail‐type systems detailed in a cocktail of metal species and cocktail of catalysts.
The following four chapters are devoted to nanoparticles in solution. In Chapters 3 and 5, the synthesis of nanoparticles in polar and green solvents (water and polyols) is described. In pure water, several applications in biphasic conditions are reviewed including hydrogenation, oxidation, and C–C coupling reactions based on the stabilization of nanoparticles with water‐soluble ligands, surfactants, and polymers (Chapter 3). All approaches in the reported chemical transformations are described under the angle of environmentally friendly and economically viable processes. Polyol media such as ethylene glycol or glycerol can act as multitask components (solvents, reductants, and stabilizers) allowing bottom‐up strategies called “polyol synthesis” for the synthesis of stable and well‐defined nanomaterials. Chapter 5 is mainly centered on metal‐based nanoparticles in polyol media synthesized by chemical approaches, but the synthesis of metal nanoparticles by sputtering techniques (top‐down methodologies) is also introduced. Chapter 4 reports the synthesis of transition metal nanoparticles in organic phase based on the decomposition of metalloorganic complexes through reduction or ligand displacement from the metal coordination sphere under mild conditions. This synthesis approach allows reaching very well‐defined metal nanoparticles that can be used as model systems for a better understanding of the structure/properties relationships. Thus, the influence of the capping ligands onto the surface properties of metal nanoparticles and consequently on their catalytic performance is discussed through a variety of examples related to hydrogenation catalysis. The formation and stabilization of various transition metal nanoparticles in ionic liquids (ILs) and their applications in catalysis under homogeneous and multiphase conditions are described in Chapter 6. Recent investigations of these soluble nanoparticles in hydrogenation of carbon dioxide as well as in the C–C coupling reaction and the hydroformylation of alkenes are highlighted.
The subsequent four chapters are dedicated to metal‐based nanoparticles deposited onto a broad variety of supports. In Chapter 7, the interest of cellulose nanocrystals (CNCs) and cellulose nanofibers (CNFs) to support metal NPs is demonstrated, evidencing that this new trend is an active and promising field of research in catalysis. In a sustainable context, nanocellulose derivatives available from biomass prove to be pertinent as renewable supports for the direct deposition and anchoring of metal nanoparticles. The use of unmodified as well as functionalized CNCs is highlighted in catalytic C–C coupling and reduction reactions. Chapter 8 describes the preparation of magnetically recoverable supported metal nanocatalysts. The deposit of various metal nanoparticles is detailed according to the nature of precursors (salts, organometallic complexes, or preformed nanoparticles). The so‐produced active species either supported onto simple iron oxide or coated with a protective layer (carbon, silica, or other oxides) exhibit excellent magnetic properties and exciting catalytic activities. Factors influencing the synthesis of metal nanoparticles supported by TEM images as well as their catalytic performances due to the nanoparticle environment (impact of ligands) are discussed in detail. In Chapter 9, recent studies on the synthesis of MOF‐supported nanoparticles are reviewed. First, it focuses on the most common methods based on a “bottom‐up” approach to generate different types of colloidal metal nanoparticles. Second, the synthetic methods of MOFs are summarized, followed by the integration methods developed to integrate metal nanoparticles into MOFs. This chapter not only provides a good understanding of the concerned topic but also highlights the advantages vs. drawbacks of respective methods. Catalytic applications of several typical metal nanoparticles/MOF composites based on their dimensional properties and structure–property relationships are fully discussed. Focused on Pt nanoparticles supported onto SBA‐15, Chapter 10 presents synthetic methodologies to deposit metal nanoparticles over silica. Interestingly, how this support can lead to superior activity as a result of tuning of the pore sizes, their interconnection or surface area for a selection of reactions is understandingly discussed. These heterogeneous nanocatalysts provide high catalytic activity in many reactions, such as oxidation, hydrogenation, and carbon–carbon coupling reactions as reported in detail.
After the review of typical synthesis of nanoparticle suspensions in various solvents in Chapters 3–6 and their deposit or inclusion in different supports (Chapters 7–10), the next three chapters are devoted to nanocatalysis. They focus on recent applications and key reactions for chemical and energy transformations including the production of hydrogen by dehydrogenation of formic acid or water‐splitting as well as eco‐respectful aspects with the transformation of biomass and CO2 into fuels or added‐value chemicals. Thus, Chapter 11 focuses on supported nanocatalysts for the hydrogenation of CO2 into fine oxygenated chemicals such as methanol, dimethyl ether, or formic acid. The mechanisms as well as new opportunities and challenges for further advancing in this research field are outlined. Relying with sustainable energy source challenge, Chapter 12 reports on the use of ruthenium‐based nanomaterials as catalysts for hydrogen production from water. In comparison with platinum catalysts, ruthenium metal or metal oxide nanoparticles have recently become widespread for the hydrogen evolution reaction (HER). This chapter highlights the key chemical factors that govern the HER performances, and the most promising electrochemical and photochemical systems are critically discussed in order to point to possible future research directions. In the strategic context of the chemical hydrogen storage, Chapter 13 reviews recent advances for hydrogen generation through the catalytic liquid‐phase dehydrogenation of formic acid in the presence of nanocatalysts including monometallic or polymetallic nanoparticles. Their advantages vs. disadvantages are discussed according to factors impacting their catalytic performances in terms of activity, selectivity, and durability.
The last two chapters are devoted to recent advances in the light of the new activation methodologies and theoretical modeling developments. Chapter 14 presents the magnetic induction and heating performances of adapted nanoscaled iron alloys to perform catalysis. This recent advance is based on the use of nanoparticles playing simultaneously the role of heating agent through magnetic hyperthermia and the role of the catalyst for a large scope of reactions based on activation of CO, CO2, and light alkanes. Thanks to a fine control of the magnetic properties of nanomaterials, the perspectives of improvement of these systems are promising and constitute a future active research field. The last chapter (Chapter 15) provides theoretical insights into metal nanocatalyst field as a result of recent progresses in computational catalysis and nanochemistry. Based on the isotropic H/D exchange and the HER activated by ruthenium nanoparticles, this contribution is a concrete case of the positive impact of computational calculations for a better understanding of the effect of the direct environment of metal nanoparticles and the reactivity changes induced by ligands in nanocatalysis.
1.3 Conclusions and Perspectives
Being dedicated to students, young researchers, and confirmed ones, this book gives a comprehensive overview on the recent advances and current trends in the engineering of metal nanoparticles – including their design, synthesis, and characterization by state‐of‐the‐art techniques – together with their various applications in catalysis. A collection of short chapters is proposed to make the reading of the whole book easier and more dynamic, while providing the main key aspects of the use of metal nanoparticles in catalysis today. Coming from a large range of institutions in different countries, the authors have been chosen for the originality of the synthesis method or of understanding approach or/and the interest toward a target catalytic application that they develop.
This book brings together the most recent achievements in the development of metal nanoparticles as catalysts by covering a selection of key aspects in this challenging domain and underlying new trends. Thus, each chapter illustrates one emerging domain of nanocatalysis with concrete applications and understanding of metal nanoparticle behavior through the presentation of the most relevant examples from the recent literature including those of the invited groups.
As it can be seen in most of the chapters of this book, a cleaner chemistry and sustainable developments are at the center of current research efforts. The use of green solvents (for instance, water, polyols, glycerol, and in a certain extent ionic liquids) as synthesis or/and reaction media has already shown to be efficient to provide highly performant nanocatalysts for diverse organic transformations. Also, the study of catalyst lifetimes (in terms of recovering, recycling, durability, and repeatability) is among the objectives of many present works. Concerning the catalytic performances, if highest possible activities are always targeted, high selectivities (both chemo‐ and stereoselectivity) have become a key point in order to limit as possible product separation steps, which are often costly regarding solvent and energy consumption. Also, the development of nanocatalysts based on earth‐abundant and cheap metals is more pertinent nowadays. This allows to face the decrease of noble metal reserves on the Earth and to reduce the catalyst costs. This is particularly relevant with regard to the scale up of catalysts for industrial processes. Beside the objective of catalyst cost reduction, a synergy effect can be expected by associating earth‐abundant metals to noble ones. The utilization of biosourced materials (such as celluloses or biochars) to build catalysts, of biosourced chemicals as new reaction media (such as lactate esters, e.g. ethyl lactate, MeTHF) or of abundant and cheap biorenewable substrates (such as terpenes, carbohydrates or agricultural residues, and vegetable oils, among others), as platforms of new synthons by organic transformations has known a huge development in nanocatalysis these past years with promising achievements. This allows not only to take advantage of natural chemicals but also to valorize certain wastes issued from biomass (for instance, woody cellulose, chitin from shellfish shells, etc.). Another important development is the use of raw chemicals issued from chemical industry (like CO2) or resulting from the increasing human activities. Concerning the improvement of catalytic transformations, which are at the basis of the production of energy vectors such as hydrogen production (either directly from water through the water‐splitting process or from dehydrogenation of formic acid that can derive from CO2), among other present challenges in this domain, nanochemistry already proved to bring powerful solutions. The transformation of CO2 into value‐added chemicals and fuels is a particularly difficult task, where metal nanocatalysts did not really emerge so far, but recent results are very encouraging, and novel nanoscale catalytic systems may meet this challenge in the near future. The application of original heating systems (hot spots obtained by magnetic induction or plasmonic excitation via the use of adequate nanocatalysts) is another strategy to limit energy consumption in catalytic organic transformations. Recent progresses in the domain of computational chemistry methods applied to metal nanoparticles proved these approaches to be very powerful and also to provide a high level of accuracy in nanocatalysis.
All these strategies provide promising perspectives and thus merit to be largely explored in order to find solutions to present challenges that chemistry world is facing and/or to open new research avenues for anticipating the future ones.
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2Introduction to Dynamic Catalysis and the Interface Between Molecular and Heterogeneous Catalysts
Alexey S. Galushko1, Alexey S. Kashin1, Dmitry B. Eremin1, Mikhail V. Polynski1, Evgeniy O. Pentsak1, Victor M. Chernyshev4, and Valentine P. Ananikov1
1Russian Academy of Sciences, N.D. Zelinsky Institute of Organic Chemistry, Leninsky Prospect 47, 119991, Moscow, Russian Federation
2University of Southern California, The Bridge@USC, 1002 Childs Way, Los Angeles, CA, 90089‐3502, USA
3Saint Petersburg State University, Universitetsky prospect 26, 198504, Saint Petersburg, Russian Federation
4Platov South‐Russian State Polytechnic University (NPI), Prosveschenya 132, 346428, Novocherkassk, Russian Federation
2.1 Introduction
Rapid progress in chemistry and nanotechnology made nanoparticle (NP) catalysis a key focus of research and industry. Organic synthesis involving nanoparticles is already well established in many laboratories. Nanoparticles used in the synthesis of drugs, dyes, molecular electronics, etc., are available in a variety of morphologies and types. These can be either zero oxidation‐state metal nanoparticles or nanosalts with a positively charged metal bound to heteroatoms [1, 2]. A given type of nanoparticles may exhibit high catalytic activity in a particular family of organic reactions and be inactive in another type of reactions [3, 4]. Investigation of catalytic activity of such nanoparticles and mechanisms of their action are a priority for both organic chemistry and catalytic science [5].
The requirements of green chemistry and improved economic efficiency, as well as the needs of basic research, support the studies of nanoscale catalytic systems. However, studying the behavior of nanoparticles in solution is complicated for several reasons. Just one type of catalyst precursor introduced into a reaction system may produce a variety of particles in solution, i.e. the chemical nature of the introduced catalyst may change under the influence of the reaction medium. Nanoparticles introduced to a solution may be transformed into soluble metal salts, while introduction of metal salts may cause formation of nanoparticles during the reaction.
Classifying the variety of newly formed particles into catalytically active and “dead weight” species is a nontrivial task that requires comprehensive investigations. This chapter provides a brief introduction into dynamic systems (including cocktail‐type systems) with a survey of methods suitable for studying the reaction mechanisms.
2.2 Dynamic Catalysis
Over the past decades, the scientific community has realized that real catalytic systems are much more complex than described by the classical concept. During the reaction, the catalyst does not retain its initial state but undergoes continuous changes. The catalyst evolution in the reaction medium modulates the reaction pathways and the mechanisms of transformation of the starting reagents into reaction products.
In cross‐coupling reactions leading to carbon–carbon bond formation, nanoscale catalysts are widely used in the form of metallic palladium – Pdn [3, 6, 7]. When Pdn nanoparticles enter the reaction mixture, they undergo oxidative addition of Ar–X (reactant) to palladium atoms followed by transfer of the resulting organometallic compound into solution [3, 8, 9]. In parallel with this, by interacting with the solvent and ligands, the nanoparticles disintegrate with the formation of nanoclusters and metal complexes (Figure 2.1a). Under the action of Ar–X, the newly formed palladium nanoclusters may further dissolve; otherwise, they may aggregate into Pdn‐type nanoparticles [4, 10]. Disintegration of nanoparticles with the transfer of complexed palladium atoms into solution is called leaching [8, 10, 11]. Mononuclear palladium species are capable of forming molecular complexes with halogen bridges and two or more palladium atoms in a complex [3]. In addition, mononuclear complexes are capable of forming nanoclusters or nanoparticles via atom‐by‐atom growth or oriented attachment. Multidirectional transitions between the various types of metal‐containing entities under the influence of the reaction medium represent the dynamic nature of the catalyst [12].
Figure 2.1 (a) Pathways of palladium particle conversion in a catalytic system (L – ligand, S – solvent, Ar – aryl, and X – halogen). (b) Type 1: a cocktail of metal species (1–3) and Type 2: a cocktail of catalysts (4–7).
Source: (b) Eremin et al. [3]; Kashin et al. [4].
Reaction systems where nanoparticles, nanoclusters, mononuclear complexes, and multicenter metal complexes are present simultaneously are called cocktail‐type systems [3, 12]. Such cocktail‐type systems can be divided into two different categories (Figure 2.1b) [3, 4]:
Type 1
. A multicomponent system containing various types of metal species with only
one
of them involved in the catalytic conversion of reagents into products is a cocktail of metal species (
Figure 2.1
b, Eqs. 1–3).
Type 2
. A multicomponent system containing various types of metal species with
more than one
of them involved in the catalytic transformation is a cocktail of catalysts (
Figure 2.1
b, Eqs. 4–7).
For instance, in C–C cross‐couplings, palladium halide molecular complexes are inactive and represent a resting state. Replacement of halogen with a different heteroatom gives a new type of nanoscale catalyst, which is effective in another type of transition‐metal‐mediated reactions. Compounds of the Pdn(XAr)m type called nanosalts are nanostructured metal salts, where X stands for heteroatom (O, S, Se, etc.). They exhibit greater efficiency in the carbon–heteroatom bond formation. The main difference of these compounds from palladium nanoparticles is the initially positive oxidation state of the metal.
The use of nanosalts as catalysts efficiently promotes selective Markovnikov‐type hydrothiolation of terminal alkynes [13]. The nanosalts are straightforwardly obtained by mixing solutions of thiol and palladium diketonate (e.g. palladium acetylacetonate), leading to immediate precipitation of [Pd(SAr)2]n. [Pd(SAr)2]n formation can be carried out in situ by introducing palladium acetylacetonate into the reaction system.
The presence of strongly coordinating ligands (e.g. acetylacetone) in the reaction system initiates nanosalt dissolution. In this type of leaching, metal dithiolate is detached from nanosalt to form [Pd(SAr)2]n−1 particles, which undergo further dissolution; 0.1 mol% of the catalyst is enough for the reaction to proceed efficiently.
Besides the catalytic applications, nanosalts can be directly used as sources of reactive organic groups. S‐Arylation can be carried out with nanostructured nickel thiolate [Ni(SAr)2]n as a starting compound [14]. This nickel salt is insoluble in the reaction medium. However, introduction of a cocatalyst in the form of Pd(OAc)2/PPh3 promotes gradual dissolution of nickel thiolate accompanied by formation of active palladium‐containing species and onset of the reaction. Advanced electron microscopy allows real‐time observations of the nanostructured salt dissolution [14, 15].
Thus, palladium nanoparticles with different oxidation states of the metal are effective catalysts for both CC and C–heteroatom bond formation reactions (Figure 2.2
