Electron beam irradiation technology: A new frontier in environmental pollution control.

With the worsening global environmental pollution, traditional pollution control methods face numerous challenges in terms of efficiency, cost and sustainability. As an emerging, efficient and eco-friendly technology, electron beam irradiation technology (EBIT) has attracted increasing attention from both academia and industry in recent years. This review systematically introduces the fundamental principles of EBIT and its primary applications in environmental pollution control, with a focus on recent research progress in wastewater treatment, air purification, solid waste degradation and heavy metal removal.

Sustainability-Inspired Upcycling of Organophosphorus Pollutants into Phosphatic Fertilizer in a Continuous-Flow Reactor.

With the increasing requirement for phosphorus resources and their shortage in nature, cyclic utilization of organophosphorus pollutants into phosphatic fertilizer might offer a sustainable approach to achieve the recycling of phosphorus. Herein, we first report the selective degradation of organophosphorus pollutants, via the synergistic effect of peroxymonosulfate (PMS) and sodium percarbonate (SPC), into phosphates (o-PO ), which are continually converted into phosphatic fertilizer by struvite precipitation on the continuous-flow reactor. Quenching experiments, electron paramagnetic resonance (EPR) results, electrochemical analysis, and density functional theory (DFT) calculation suggest that the transfer of electrons from SPC to PMS results in the synthesis of catalytically active species (i.

Single-molecule resolution of macromolecules with nanopore devices.

Nanopore-based electrical detection technology holds single-molecule resolution and combines the advantages of high sensitivity, high throughput, rapid analysis, and label-free detection. It is widely applied in the determination of organic and biological macromolecules, small molecules, and nanomaterials, as well as in nucleic acid and protein sequencing. There are a wide variety of organic polymers and biopolymers, and their chemical structures, and conformation in solution directly affect their ensemble properties.

Single-molecule resolution of the conformation of polymers and dendrimers with solid-state nanopores.

Polymers and dendrimers are macromolecules, possessing unique and intriguing characteristics, that are widely applied in self-assembled functional materials, green catalysis, drug delivery and sensing devices. Traditional approaches for the structural characterization of polymers and dendrimers involve DLS, GPC, NMR, IR and TG, which provide their physiochemical features and ensemble information, whereas their unimolecular conformation and dispersion also are key features allowing to understand their transporting profile in confined ionic nanochannels. This work demonstrates the nanopore approach for the determination of charged homopolymers, neutral block copolymer and dendrimers under distinct bias potentials and pH conditions.

Experimental and Theoretical Insights into Single Atoms, Dual Atoms, and Sub-Nanocluster Catalysts for Electrochemical CO Reduction (CORR) to High-Value Products.

Electrocatalytic carbon dioxide (CO) conversion into valuable chemicals paves the way for the realization of carbon recycling. Downsizing catalysts to single-atom catalysts (SACs), dual-atom catalysts (DACs), and sub-nanocluster catalysts (SNCCs) has generated highly active and selective CO transformation into highly reduced products. This is due to the introduction of numerous active sites, highly unsaturated coordination environments, efficient atom utilization, and confinement effect compared to their nanoparticle counterparts.

Unveiling Hierarchical Self-Assembly of Triazolylferrocenyl Dendrimers: Producing Non-Traditional Intrinsically Green Fluorescent Vesosomes for Nanotheranostics.

Dendrimers and supramolecular chemistry continue to fascinate researchers due to the endless unrevealed potential of their combination. This study investigates the self-assembly process of a series of hydrophobic triazolylferrocenyl dendrimers in aqueous medium. Deep investigation through NMR spectroscopy, absorption UV-vis spectroscopy along with theoretical simulations demonstrates that the ferrocenyl moieties interact intramolecularly and intermolecularly driving the self-assembly process.

Niobic acid as a support for microheterogeneous nanocatalysis of sodium borohydride hydrolysis under mild conditions.

This study explores the stabilization by niobic acid, of Pt, Ni, Pd, and Au nanoparticles (NPs) for the efficient microheterogeneous catalysis of NaBH hydrolysis for hydrogen production. Niobic acid is the most widely studied NbO polymorph, and it is employed here for the first time for this key reaction relevant to green energy. Structural insights from XRD, Raman, and FTIR spectroscopies, combined with hydrogen production data, reveal the role of niobic acid's Brønsted acidity in its catalytic activity.

Cu(I)-Glutathione Assembly Supported on ZIF-8 as Robust and Efficient Catalyst for Mild CO 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 calculation, affords CO 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.

Biomass substrate-derived graphene-like N-doped porous carbon nanosheet-supported PtCo nanocatalyst for efficient and selective hydrogenation of unsaturated furanic aldehydes.

Unsaturated furanic aldehydes are derived from lignocellulosic biomass resources and subsequently used to produce valuable chemicals. However, the highly efficient, selective hydrogenation of the biomass-derived unsaturated furan CO bond remains challenging. Here we report that graphene-like nitrogen doped porous carbon (GNPC) nanosheets are synthesized from carbon-rich, sustainable, and renewable biomass precursors (glucose, fructose and 5-hydroxymethylfurfural, HMF) with high surface areas, large pore volumes and narrow mesopores.

Using waste to treat waste: facile synthesis of hollow carbon nanospheres from lignin for water decontamination.

Lignin, the most abundant natural material, is considered as a low-value commercial biomass waste from paper mills and wineries. In an effort to turn biomass waste into a highly valuable material, herein, a new-type of hollow carbon nanospheres (HCNs) is designed and synthesized by pyrolysis of biomass dealkali lignin, as an efficient nanocatalyst for the elimination of antibiotics in complex water matrices. Detailed characterization shows that HCNs possess a hollow nanosphere structure, with abundant graphitic C/N and surface N and O-containing functional groups favorable for peroxydisulfate (PDS) activation.

Theoretically Designed CuSn-Cu-SnO as Three-Component Electrocatalyst for Efficient and Tunable CO Reduction to Syngas.

Electrocatalytic transformation of CO 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 CuSn-Cu-SnO that addresses this challenge is presented.

Ferrocene-Based Drugs, Delivery Nanomaterials and Fenton Mechanism: State of the Art, Recent Developments and Prospects.

Ferrocene has been the most used organometallic moiety introduced in organic and bioinorganic drugs to cure cancers and various other diseases. Following several pioneering studies, two real breakthroughs occurred in 1996 and 1997. In 1996, Jaouen et al.

From sandwich complexes to dendrimers: journey toward applications to sensing, molecular electronics, materials science, and biomedicine.

This review links various areas of inorganic chemistry around the themes developed by our research group during the last four decades. It is firstly based on the electronic structure of iron sandwich complexes, showing how the metal electron count dictates their reactivities, with various applications ( C-H activation, C-C bond formation) as reducing and oxidizing agents, redox and electrocatalysts and precursors of dendrimers and catalyst templates through bursting reactions. Various electron-transfer processes and consequences are explored, including the influence of the redox state on the acidity of robust ligands and the possibility to iterate C-H activation and C-C bond formation to build arene-cored dendrimers.

Facile MOF Support Improvement in Synergy with Light Acceleration for Efficient Nanoalloy-Catalyzed H Production from Formic Acid.

Hydrogen (H) generation and storage are actively investigated to provide a green source of energy, and formic acid (HCOOH), a major product obtained from the biomass, is regarded as a productive source of H. Therefore, improvements in heterogeneous catalysts are called for. Here, a novel type of catalyst support is proposed involving simple addition of the mixture of metal ion precursors to core-shell ZIF-8@ZIF-67, followed by reduction with NaBH, with performances surpassing those obtained using nanocatalysts in ZIF-8 or ZIF-67.

Triazole-functionalized hydrochar-stabilized Pd nanocatalyst for ullmann coupling.

Biomass valorization is essential, particularly in emerging countries. Here, hydrochar from arabica coffee straw was functionalized with a triazole group (HD-TRz) for use as a support of palladium nanoparticles (PdNPs-HD-TRz) applied in the Ullmann coupling reaction for the first time. It provided remarkably excellent selectivities, conversions at a temperature as low as 45 °C and catalyst recyclability, surpassing previous literature performances.

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.

Looking at platinum carbonyl nanoclusters as .

Although the chemistry of carbonyl-protected platinum nanoclusters is well established, their bonding mode remains poorly understood. In most of them, the average Pt oxidation state is zero or slightly negative, leading to the apparent average configuration 5d 6s ( = 0 or very small) and the apparent conclusion that metal-metal bonding cannot arise from the completely filled 5d shell nor from the empty (or almost empty) 6s orbitals. However, DFT calculations show in fact that in these species the actual average configuration is 5d 6s, which provides to the whole cluster a significant total number of 6s electrons that ensures metal-metal bonding.

Turning waste into wealth: facile and green synthesis of carbon nanodots from pollutants and applications to bioimaging.

In an effort to turn waste into wealth, Reactive Red 2 (RR2), a common and refractory organic pollutant in industrial wastewater, has been employed for the first time as a precursor to synthesize carbon nanodots (CNDs) by a facile, green and low-cost route, without utilization of any strong acids or other oxidizers. The detailed characterizations have confirmed that the synthesized CNDs exhibit good water dispersibility, with a mean particle size of 2.43 nm and thickness of 1-3 layers.

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.

Ferrocenyl-terminated polyphenylene-type "click" dendrimers as supports for efficient gold and palladium nanocatalysis.

Although dendrimer supports have been known as key parts of nanocatalysts, the capability of rigid dendrimers for this function has not yet been reported. Here, the study is focused on ferrocenylmethylenetriazolyl-terminated dendrimers (FcMTPD) as supports of remarkably efficient nanogold and nanopalladium catalysts. A biphasic system is elaborated to evaluate the catalytic activity of FcMTPD-supported Au and Pd nanoparticles (NPs) for the reduction of 4-nitrophenol to 4-aminophenol by NaBH at 20 °C, and FcMTPD-supported PdNPs are found to be the best nanocatalysts with a rate constant k = 7.

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.

New atomically precise (M = Au/Ag) nanoclusters as excellent oxygen reduction reaction catalysts.

By introducing 1,1'-bis-(diphenylphosphino)ferrocene (dppf) as an activating ligand, two novel nanoclusters, (M = Au/Ag), have been controllably synthesized and structurally characterized. The atomically precise structures of the nanoclusters were determined by SCXC and further confirmed by ESI-TOF-MS, TGA, XPS, DPV, and FT-IR measurements. The nanoclusters supported on activated carbon (C) are exploited as efficient oxygen reduction reaction (ORR) catalysts in alkaline solutions.

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.

ROMP Synthesis of Side-Chain Ferrocene-Containing Polyelectrolyte and Its Redox-Responsive Hydrogels Showing Dramatically Improved Swelling with β-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 β-CD aqueous solution to form β-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 β-CD@Fc inclusion complexes.