Cu(I)-Glutathione Assembly Supported on ZIF-8 as Robust and Efficient Catalyst for Mild CO2 Conversions.

The Cu-glutathione (GSH) redox system, essential in biology, is designed here as a supramacromolecular assembly in which the tetrahedral 18e Cu(I) center loses a thiol ligand upon adsorption onto ZIF-8, as shown by EXAFS and DFT calculation, to generate a very robust 16e planar trigonal single-atom Cu(I) catalyst. Synergy between Cu(I) and ZIF-8, revealed by catalytic experiments and DFT, affords CO2 conversion into high-value-added chemicals with a wide scope of substrates by reaction with terminal alkynes or propargyl amines in excellent yields under mild conditions and reuse at least 10 times without significant decrease in catalytic efficiency.

Theoretically Designed Cu10 Sn3 -Cu-SnOx as Three-Component Electrocatalyst for Efficient and Tunable CO2 Reduction to Syngas.

Electrocatalytic transformation of CO2 to various syngas compositions is an exceedingly attractive approach to carbon-neutral recycling. Meanwhile, the achievement of selectivity, stability, and tunability of product ratios using single-component electrocatalysts is challenging. Herein, the theoretically-assisted design of the triple-component nanocomposite electrocatalyst Cu10 Sn3 -Cu-SnOx that addresses this challenge is presented. It is shown that Cu10 Sn3 is a valuable electrocatalyst for suitable CO2 reduction to CO, SnO2 for CO2 reduction to formate at large overpotentials, and that the Cu-SnO2 interface facilitates H2 evolution. Accordingly, the interaction between the three functional components affords tunable CO/H2 ratios, from 1:2 to 2:1, of the produced syngas by controlling the applied potentials and relative contents of functional components. The syngas generation is selective (Faradaic efficiency, FE = 100%) at relatively lower cathodic potentials, whereas formate is the only liquid product detected at relatively higher cathodic potentials. The theoretically guided design approach therefore provides a new opportunity to boost the selectivity and stability of CO2 reduction to tunable syngas.

Exploiting the Fracture in Metal-Organic Frameworks: A General Strategy for Bifunctional Atom-Precise Nanocluster/ZIF-8(300 °C) Composites.

Atom-precise nanoclusters-metal-organic framework (APNC/MOF) composites, as bifunctional material with well-defined structures, have attracted considerable attention in recent years. Despite the progress made to date, there is an urgent need to develop a generic and scalable approach for all APNCs. Herein, the authors present the Exploiting Fracture Strategy (EFS) and successfully construct a super-stable bifunctional APNC/ZIF-8(300 °C) composite overcoming the limitations of previous strategies in selecting APNCs. The EFS utilizes the fracture of ZnN in ZIF-8 after annealing at 300 °C. This method is suitable for all kinds of S/P protected APNCs with different sizes, including uncharged clusters Au1 Ag39 , Ag40 , negatively charged Au12 Ag32 , positively charged Ag46 Au24 , Au4 Cu4 and P-ligand-protected Pd3 Cl. Importantly, the generated APNC/MOF show significantly improved performances, for example, the activities of Au12 Ag32 /ZIF-8(300°C), Au4 Cu4 /ZIF-8(300°C), and Au1 Ag39 /ZIF-8(300°C) in the corresponding reactions are higher than those of Au12 Ag32 , Au4 Cu4 , and Au1 Ag39 , respectively. In particular, Au12 Ag32 /ZIF-8(300 °C) shows higher activity than Au12 Ag32 @ZIF-8. Therefore, this work offers guidance for the design of bifunctional APNC/MOF composites with excellent optimization of properties and opens up new horizons for future related nanomaterial studies and nanocatalyst designs.

State of the Art and Prospects in Metal-Organic Framework (MOF)-Based and MOF-Derived Nanocatalysis.

Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.

Atomically Precise Noble Metal Nanoclusters as Efficient Catalysts: A Bridge between Structure and Properties.

Improving the knowledge of the relationship between structure and properties is fundamental in catalysis. Recently, researchers have developed a variety of well-controlled methods to synthesize atomically precise metal nanoclusters (NCs). NCs have shown high catalytic activity and unique selectivity in many catalytic reactions, which are related to their ultrasmall size, abundant unsaturated active sites, and unique electronic structure different from that of traditional nanoparticles (NPs). More importantly, because of their definite structure and monodispersity, they are used as model catalysts to reveal the correlation between catalyst performance and structure at the atomic scale. Therefore, this review aims to summarize the recent progress on NCs in catalysis and provide potential theoretical guidance for the rational design of high-performance catalysts. First a brief summary of the synthetic strategies and characterization methods of NCs is provided. Then the primary focus of this review-the model catalyst role of NCs in catalysis-is illustrated from theoretical and experimental perspectives, particularly in electrocatalysis, photocatalysis, photoelectric conversion, and catalysis of organic reactions. Finally, the main challenges and opportunities are examined for a deep understanding of the key catalytic steps with the goal of expanding the catalytic application range of NCs.

Recent developments of nanocatalyzed liquid-phase hydrogen generation.

Hydrogen is the most effective and sustainable carrier of clean energy, and liquid-phase hydrogen storage materials with high hydrogen content, reversibility and good dehydrogenation kinetics are promising in view of "hydrogen economy". Efficient, low-cost, safe and selective hydrogen generation from chemical storage materials remains challenging, however. In this Review article, an overview of the recent achievements is provided, addressing the topic of nanocatalysis of hydrogen production from liquid-phase hydrogen storage materials including metal-boron hydrides, borane-nitrogen compounds, and liquid organic hydrides. The state-of-the-art catalysts range from high-performance nanocatalysts based on noble and non-noble metal nanoparticles (NPs) to emerging single-atom catalysts. Key aspects that are discussed include insights into the dehydrogenation mechanisms, regenerations from the spent liquid chemical hydrides, and tandem reactions using the in situ generated hydrogen. Finally, challenges, perspectives, and research directions for this area are envisaged.

Insight into the Mechanism of the CuAAC Reaction by Capturing the Crucial Au4Cu4-π-Alkyne Intermediate.

The classic Fokin mechanism of the CuAAC reaction of terminal alkynes using a variety of Cu(I) catalysts is well-known to include alkyne deprotonation involving a bimetallic σ,π-alkynyl intermediate. In this study, we have designed a CNT-supported atomically precise nanocluster Au4Cu4 (noted Au4Cu4/CNT) that heterogeneously catalyzes the CuAAC reaction of terminal alkynes without alkyne deprotonation to a σ,π-alkynyl intermediate. Therefore, three nanocluster-π-alkyne intermediates [Au4Cu4(π-CH≡C-p-C6H4R)], R = H, Cl, and CH3, have been captured and characterized by MALDI-MS. This Au4Cu4/CNT system efficiently catalyzed the CuAAC reaction of terminal alkynes, and internal alkynes also undergo this reaction. DFT results further confirmed that HC≡CPh was activated by π-complexation with Au4Cu4, unlike the classic dehydrogenation mechanism involving the bimetallic σ,π-alkynyl intermediate. On the other hand, a Cu11/CNT catalyst was shown to catalyze the reaction of terminal alkynes following the classic deprotonation mechanism, and both Au11/CNT and Cu11/CNT catalysts were inactive for the AAC reaction of internal alkynes under the same conditions, which shows the specificity of Au4Cu4 involving synergy between Cu and Au in this precise nanocluster. This will offer important guidance for subsequent catalyst design.

Self-Assembly of a Triazolylferrocenyl Dendrimer in Water Yields Nontraditional Intrinsic Green Fluorescent Vesosomes for Nanotheranostic Applications.

The promising field of nanomedicine stimulates a continuous search for multifunctional nanotheranostic systems for imaging and drug delivery. Herein, we demonstrate that application of supramolecular chemistry's concepts in dendritic assemblies can enable the formation of advanced dendrimer-based nanotheranostic devices. A dendrimer bearing 81 triazolylferrocenyl terminal groups adopts a more compact shell-like structure in polar solvents with the ferrocenyl peripheral groups backfolding toward the hydrophobic dendrimer interior, while exposing the more polar triazole moieties as the dendritic shell. Akin to lipids, the compact dendritic structure self-assembles into uniform nanovesicles that in turn self-assemble into larger vesosomes in water. The vesosomes emit green nontraditional intrinsic fluorescence (NTIL), which is an emerging property as there are no classical fluorophores in the dendritic macromolecular structure. This work confirms the hypothesis that the NTIL emission is greatly enhanced by rigidification of the supramolecular assemblies containing heteroatomic subluminophores (HASLs) and by the presence of electron rich functional groups on the periphery of dendrimers. This work is the first one detecting NTIL in ferrocenyl-terminated dendrimers. Moreover, the vesosomes are stable in biological medium, are uptaken by cells, and show cytotoxic activity against cancer cells. Accordingly, the self-organization of these dendrimers into tertiary structures promotes the emergence of new properties enabling the same component, in this case, ferrocenyl group, to function as both antitumoral drug and fluorophore.

Hydrogen Generation upon Nanocatalyzed Hydrolysis of Hydrogen-Rich Boron Derivatives: Recent Developments.

ConspectusProduction of hydrogen from nonfossil sources is essential toward the generation of sustainable energy. Hydrogen generation upon hydrolysis of stable hydrogen-rich materials has long been proposed as a possibility of hydrogen disposal on site, because transport of explosive hydrogen gas is dangerous. Hydrolysis of some boron derivatives could rapidly produce large amounts of hydrogen, but this requires the presence of very active catalysts. Indeed, late transition-metal nanocatalysts have recently been developed for the hydrolysis of a few hydrogen-rich precursors.Our research group has focused on the improvement and optimization of highly performing Earth-abundant transition-metal-based nanocatalysts, optimization of remarkable synergies between different metals in nanoalloys, supports including positive synergy with nanoparticles (NPs) for rapid hydrogen generation, comparison between various endo- or exoreceptors working as homogeneous and heterogeneous supports, mechanistic research, and comparison of the nanocatalyzed hydrolysis of several boron hydrides.First, hydrogen production upon hydrolysis of ammonia borane, AB (3 mol H2 per mol AB) was examined with heterogeneous endoreceptors. Thus, a highly performing Ni@ZIF-8 nanocatalyst was found to be superior over other Earth-abundant nanocatalysts and supports. With 85.7 molH2·molcat-1·min-1 at 25 °C, this Ni nanocatalyst surpassed the results of previous Earth-abundant nanocatalysts. The presence of NaOH accelerated the reaction, and a remarkable pH-dependent "on-off" control of the H2 production was established. Bimetallic nanoalloys Ni-Pt@ZIF-8 showed a dramatic volcano effect optimized with a nanoalloy containing 2/3 Ni and 1/3 Pt. The rate reached 600 molH2·molcat-1·min-1 and 2222 molH2·molPt-1·min-1 at 20 °C, which much overtook the performances of both related nanocatalysts Ni@ZIF-8 and Pt@ZIF-8. Next, hydrogen production was also researched via hydrolysis of sodium borohydride (4 mol H2 per mol NaBH4) using nanocatalysts in ZIF-8, and, among Earth-abundant nanocatalysts, Co@ZIF-8 showed the best performance, outperforming previous Co nanocatalysts. For exoreceptors, "click" dendrimers containing triazole ligands on their tripodal tethers were used as supports for homogeneous (semiheterogeneous) catalysis of both AB and NaBH4 hydrolysis. For both reactions, Co was found to be the best Earth-abundant metal, Pt the best noble metal, and Co1Pt1 the best nanoalloy, with synergistic effects. Based on kinetic measurements and kinetic isotope effects for all of these reactions, mechanisms are proposed and the hydrogen produced was further used in tandem reactions. Overall, dramatic triple synergies between these nanocatalyst components have allowed hydrogen release within a few seconds under ambient conditions. These nanocatalyst improvements and mechanistic findings should also inspire further nanocatalyst design in various areas of hydrogen production.

On the Roles of Electron Transfer in Catalysis by Nanoclusters and Nanoparticles.

Electron transfer plays a major role in chemical reactions and processes, and this is particularly true of catalysis by nanomaterials. The advent of metal nanoparticle (NP) catalysts, recently including atomically precise nanoclusters (NCs) as parts of nanocatalyst devices has brought increased control of the relationship between NP and NC structures and their catalytic functions. Consequently, the molecular definition of these new nanocatalysts has allowed a better understanding and management of various kinds of electron transfer involved in the catalytic processes. This Minireview brings a chemist's view of several major aspects of electron-transfer functions concerning NPs and NCs in catalytic processes. Particular focus concerns the role of NPs and NCs as electron reservoirs and light-induced antenna in catalytic processes from H2 generation to more complex reactions and sustainable energy production.

ROMP Synthesis of Side-Chain Ferrocene-Containing Polyelectrolyte and Its Redox-Responsive Hydrogels Showing Dramatically Improved Swelling with ß-Cyclodextrin.

A new side-chain ferrocene (Fc)-containing polyelectrolyte has been synthesized by controlled ring-opening metathesis polymerization of a water-soluble Fc-containing norbornene-based quaternary ammonium salt, as well as the corresponding covalently cross-linked polyelectrolyte hydrogel. In order to provide Fc-containing supramolecular polyelectrolyte hydrogels whose swelling property is largely improved by host-guest interaction, a covalently cross-linked polyelectrolyte hydrogel is soaked into the ß-CD aqueous solution to form ß-CD@Fc supramolecular polyelectrolyte hydrogel, or alternatively the quaternary ammonium salt supramolecular monomer is first formed, then copolymerized with a crosslinking agent to fabricate the supramolecular hydrogel with better water absorption ability. All the Fc-containing hydrogels exhibited good redox-responsiveness with swelling-shrinking behaviors by chemically reversibly adjusting the disassembly/assembly of ß-CD@Fc inclusion complexes. This is the first example of side-chain Fc-containing polycationic supramolecular hydrogels possessing swelling-shrinking properties based on the splitting/combining of ß-CD and Fc units, and potential applications are expected as controlled drug delivery and actuators.

The Metallocene Battery: Ultrafast Electron Transfer Self Exchange Rate Accompanied by a Harmonic Height Breathing.

The first all-metallocene rechargeable battery consisting of poly-cobaltocenium/- and poly-ferrocene/reduced graphene oxide composites as anode and cathode was prepared. The intrinsically fast ET self-exchange rate of metallocenes was successfully combined with an efficient ion-percolation achieved by molecular self-assembly. The resulting battery materials show ideal Nernstian behavior, is thickness scalable up to >1.2 C cm-2 , and exhibit high coulombic efficiency at ultrafast rates (200 A g-1 ). Using aqueous LiClO4 , the charge is carried exclusively by the anion. The ClO4 - intercalation is accompanied by a reciprocal height change of the active layers. Principally, volume changes in organic battery materials during charging/discharging are not desirable and represent a major safety issue. However, here, the individual height changes-due to ion breathing-are reciprocal and thus prohibiting any internal pressure build-up in the closed-cell, leading to excellent cycling stability.

Design and Remarkable Efficiency of the Robust Sandwich Cluster Composite Nanocatalysts ZIF-8@Au25@ZIF-67.

Heterogeneous catalysts with precise surface and interface structures are of great interest to decipher the structure-property relationships and maintain remarkable stability while achieving high activity. Here, we report the design and fabrication of the new sandwich composites ZIF-8@Au25@ZIF-67[tkn] and ZIF-8@Au25@ZIF-8[tkn] [tkn = thickness of shell] by coordination-assisted self-assembly with well-defined structures and interfaces. The composites ZIF-8@Au25@ZIF-67 efficiently catalyzed both 4-nitrophenol reduction and terminal alkyne carboxylation with CO2 under ambient conditions with remarkably improved activity and stability, compared to the simple components Au25/ZIF-8 and Au25@ZIF-8, highlighting the highly useful function of the ultrathin shell. In addition, the performances of these composite sandwich catalysts are conveniently regulated by the shell thickness. This concept and achievements should open a new avenue to the targeted design of well-defined nanocatalysts with enhanced activities and stabilities for challenging reactions.

Theoretical Analysis of the Mackay Icosahedral Cluster Pd55 (PiPr3 )12 (µ3 -CO)20 : An Open-Shell 20-Electron Superatom.

The electronic structure of the spherical Mackay icosahedral nanosized cluster Pd55 (PiPr3 )12 (µ3 -CO)20 is analyzed by using DFT calculations. Results reveal that it can be considered as a regular superatom with a "magic" electron count of 20, characterized by a 1S2 1P6 1D10 2S2 jellium configuration. Its open shell nature is associated with partial occupation of non-jellium, 4d-type, levels located on the interior of the Pd55 kernel. This shows that the superatom model can be used to rationalize the bonding and stability of spherical ligated group 10 clusters, despite their apparent 0-electron count.

Metallopolymers for advanced sustainable applications.

Since the development of metallopolymers, there has been tremendous interest in the applications of this type of materials. The interest in these materials stems from their potential use in industry as catalysts, biomedical agents in healthcare, energy storage and production as well as climate change mitigation. The past two decades have clearly shown exponential growth in the development of many new classes of metallopolymers that address these issues. Today, metallopolymers are considered to be at the forefront for discovering new and sustainable heterogeneous catalysts, therapeutics for drug-resistant diseases, energy storage and photovoltaics, molecular barometers and thermometers, as well as carbon dioxide sequesters. The focus of this review is to highlight the advances in design of metallopolymers with specific sustainable applications.

Highly Selective and Sharp Volcano-type Synergistic Ni2Pt@ZIF-8-Catalyzed Hydrogen Evolution from Ammonia Borane Hydrolysis.

Ammonia borane hydrolysis is considered as a potential means of safe and fast method of H2 production if it is efficiently catalyzed. Here a series of nearly monodispersed alloyed bimetallic nanoparticle catalysts are introduced, optimized among transition metals, and found to be extremely efficient and highly selective with sharp positive synergy between 2/3 Ni and 1/3 Pt embedded inside a zeolitic imidazolate framework (ZIF-8) support. These catalysts are much more efficient for H2 release than either Ni or Pt analogues alone on this support, and for instance the best catalyst Ni2Pt@ZiF-8 achieves a TOF of 600 molH2·molcatal-1·min-1 and 2222 molH2·molPt-1·min-1 under ambient conditions, which overtakes performances of previous Pt-base catalysts. The presence of NaOH boosts H2 evolution that becomes 87 times faster than in its absence with Ni2Pt@ZiF-8, whereas NaOH decreases H2 evolution on the related Pt@ZiF-8 catalyst. The ZIF-8 support appears outstanding and much more efficient than other supports including graphene oxide, active carbon and SBA-15 with these nanoparticles. Mechanistic studies especially involving kinetic isotope effects using D2O show that cleavage by oxidative addition of an O-H bond of water onto the catalyst surface is the rate-determining step of this reaction. The remarkable catalyst activity of Ni2Pt@ZiF-8 has been exploited for successful tandem catalytic hydrogenation reactions using ammonia borane as H2 source. In conclusion the selective and remarkable synergy disclosed here together with the mechanistic results should allow significant progress in catalyst design toward convenient H2 generation from hydrogen-rich substrates in the close future.

Electron- and Hydride-Reservoir Organometallics as Precursors of Catalytically Efficient Transition Metal Nanoparticles in Water.

Nanoparticles (NPs) are actively investigated for their efficient use in catalysis, but their means of synthesis is a key factor influencing their catalytic properties owing to surface coverage with byproducts. Here, neutral electron- and hydride-rich late transition metal organometallics are compared for the synthesis of late transition metal NPs in the presence of poly(vinylpirolidone) (PVP). In particular, the effect of electron-reservoir donors, hydride-reservoir donors, and electron-rich dimers yielding NPs electrostatically stabilized by cationic organometallics are compared in terms of NP size and catalytic efficiency. The catalytic reactions scrutinized with excellent results include 4-nitrophenol reduction to 4-aminophenol by NaBH4 for the AuNPs and PdNPs, and Suzuki-Miyaura reactions for the PdNPs. The nature of the reductant has more influence on the NP size in the case of AuNPs than PdNPs, and the best NP catalysts are obtained with hydride-reservoir complexes as reductants. The less bulky hydride donors are superior, with the complex [CoCp(ŋ4 -C5 H6 )] (Cp=ŋ5 -C5 H5 ) giving the NPs with the best catalyst efficiencies for both reactions. Protection of the NP cores by the organometallic sandwich salt is found to be the key to catalytic efficiency.

Electron Flow in Large Metallomacromolecules and Electronic Switching of Nanoparticle Stabilization: Click Ferrocenyl Dentromers that Reduce AuIII to Au Nanoparticles.

Click ferrocenyl-terminal dentromers, a family of arene-cored dendrimers with triple branching (9-Fc, 27-Fc, 81-Fc, and 243-Fc), reduce AuIII to ferricinium dentromer-stabilized Au nanoparticles (AuNPs). Cyclic voltammetry studies in CH2 Cl2 show reversible CV waves with some adsorption for the 243-Fc dentromer and the number of redox groups found, 255±25, by using the Bard-Anson method, is close to the theoretical number of 243. The dentromers reduce aqueous HAuCl4 to water-soluble ferricinium chloride dentromer-stabilized AuNPs with core sizes between 30 and 47 nm. These triazolylferricinium dentromer-stabilized AuNPs are reduced by cobaltocene to cobalticinium chloride and ferrocene dentromer weakly stabilized AuNPs together with a redshift of the AuNP plasmon. The weakness of the AuNP stabilization is characterized by dentromer extraction with CH2 Cl2 along with irreversible AuNP agglomeration for the 9, 27, and 81-ferrocenyl dentromer, with only the 243-ferrocenyl dentromer-AuNP withstanding this process. Altogether, this demonstrates the electronic switching of the dentromer-mediated AuNP stabilization.

The recent development of efficient Earth-abundant transition-metal nanocatalysts.

Whereas noble metal compounds have long been central in catalysis, Earth-abundant metal-based catalysts have in the same time remained undeveloped. Yet the efficacy of Earth-abundant metal catalysts was already shown at the very beginning of the 20th century with the Fe-catalyzed Haber-Bosch process of ammonia synthesis and later in the Fischer-Tropsch reaction. Nanoscience has revolutionized the world of catalysis since it was observed that very small Au nanoparticles (NPs) and other noble metal NPs are extraordinarily efficient. Therefore the development of Earth-abundant metals NPs is more recent, but it has appeared necessary due to their "greenness". This review highlights catalysis by NPs of Earth-abundant transition metals that include Mn, Fe, Co, Ni, Cu, early transition metals (Ti, V, Cr, Zr, Nb and W) and their nanocomposites with emphasis on basic principles and literature reported during the last 5 years. A very large spectrum of catalytic reactions has been successfully disclosed, and catalysis has been examined for each metal starting with zero-valent metal NPs followed by oxides and other nanocomposites. The last section highlights the catalytic activities of bi- and trimetallic NPs. Indeed this later family is very promising and simultaneously benefits from increased stability, efficiency and selectivity, compared to monometallic NPs, due to synergistic substrate activation.

Dentromers, a Family of Super Dendrimers with Specific Properties and Applications.

Dentromers (from dentro, δεντρο: tree in Greek), and meros (µÎµροσ, in greek: part) are introduced as a family of dendrimers constructed according to successive divergent 1 → 3 branching. The smaller dentromers have 27 terminal branches. With alcohol termini they were originally named arborols by Newkome, who pioneered 1 → 3 constructions of dendrimers and dendrons. Giant dentromers have been constructed and decorated in particular with ferrocene and other redox active groups. The synthesis, specific properties, and applications are examined in this mini review article dedicated to Don Tomalia, with an emphasis on dense peripheral packing favoring the functions of encapsulation, redox sensing, and micellar template for catalysis in water and aqueous solvents.