Hot Carrier Lifetimes and Electrochemical Water Dissociation Enhanced by Nickel Doping of a Plasmonic Electrocatalyst.

Hot carriers generated by localized surface plasmon resonance (LSPR) excitation of plasmonic metal nanoparticles are known to enhance electrocatalytic reactions. However, the participation of plasmonically generated carriers in interfacial electrochemical reactions is often limited by fast relaxation of these carriers. Herein, we address this challenge by tuning the electronic structure of a plasmonic electrocatalyst. Specifically, we design an electrocatalyst for alkaline hydrogen evolution reaction (HER) that consists of nanoparticles of a ternary Cu-Pt-Ni ternary alloy. The CuPt alloy has both plasmonic attributes and electrocatalytic HER activity. Ni doping contributes an electron-deficient 3d band and fully filled 4s band, which promotes water adsorption and prolongs the lifetimes of excited carriers generated by plasmonic excitation. As an outcome, the Cu-Pt-Ni nanoparticles exhibit boosted activity for electrochemical water dissociation and HER under LSPR excitation.

Convex Cube-Shaped Pt34 Fe5 Ni20 Cu31 Mo9 Ru High Entropy Alloy Catalysts toward High-Performance Multifunctional Electrocatalysis.

High entropy alloy (HEA) catalysts exhibit excellent multifunctional catalytic performance due to the synergistic effect of multi-metal components. However, shape-controlled synthesis of such kinds of HEA catalysts, especially those with high index facets, still faces great challenges, limiting further enhancement of their catalytic performance. Herein, one-pot synthesis of convex cube-shaped Pt34 Fe5 Ni20 Cu31 Mo9 Ru HEA catalysts which possess rich (310) facets and a diagonal crystalline size of 38.5 nm is reported. Transmission electron microscopy measurements indicate cube-shaped nanocrystals are obtained first and further selective growth of pyramid on each facet of the cube-shaped nanocrystal results in a convex cube shape. Pt34 Fe5 Ni20 Cu31 Mo9 Ru HEA catalysts show excellent electrocatalytic performance toward the oxygen reduction reaction (ORR), hydrogen evolution reaction (HER), and oxygen evolution reaction (OER), which exhibit a half-wave potential of 0.87 V for ORR in 0.1 m HClO4 , and overpotential of 20 and 259 mV for HER and OER at a current density of 10 mA cm-2 in an alkaline medium. A control experiment and density functional theory calculation indicate that the Ru element plays a decisive role in both the formation of the convex cube shape and also the high catalytic performance.

Self-Stabilized and Strongly Adhesive Supramolecular Polymer Protective Layer Enables Ultrahigh-Rate and Large-Capacity Lithium-Metal Anode.

Constructing a solid electrolyte interface (SEI) is a highly effective approach to overcome the poor reversibility of lithium (Li) metal anodes. Herein, an adhesive and self-healable supramolecular copolymer, comprising of pendant poly(ethylene oxide) (PEO) segments and ureido-pyrimidinone (UPy) quadruple-hydrogen-bonding moieties, is developed as a protection layer of Li anode by a simple drop-coating. The protection performance of in-situ-formed LiPEO-UPy SEI layer is significantly enhanced owing to the strong binding and improved stability arising from a spontaneous reaction between UPy groups and Li metal. An ultrathin (approximately 70 nm) LiPEO-UPy layer can contribute to stable and dendrite-free cycling at a high areal capacity of 10 mAh cm-2 at 5 mA cm-2 for 1000 h. This coating together with the promising electrochemical performance offers a new strategy for the development of dendrite-free metal anodes.

Synergy between Plasmonic and Electrocatalytic Activation of Methanol Oxidation on Palladium-Silver Alloy Nanotubes.

Localized surface plasmon resonance (LSPR) excitation of noble metal nanoparticles has been shown to accelerate and drive photochemical reactions. Here, LSPR excitation is shown to enhance the electrocatalysis of a fuel-cell-relevant reaction. The electrocatalyst consists of Pdx Ag alloy nanotubes (NTs), which combine the catalytic activity of Pd toward the methanol oxidation reaction (MOR) and the visible-light plasmonic response of Ag. The alloy electrocatalyst exhibits enhanced MOR activity under LSPR excitation with significantly higher current densities and a shift to more positive potentials. The modulation of MOR activity is ascribed primarily to hot holes generated by LSPR excitation of the Pdx Ag NTs.

Point of Anchor: Impacts on Interfacial Charge Transfer of Metal Oxide Nanoparticles.

Photoinduced charge transfer across the metal oxide-organic ligand interface plays a key role in the diverse applications of metal oxide nanomaterials/nanostructures, such as photovoltaics, photocatalysis, and optoelectronics. Thus far, most studies are focused on molecular engineering of the organic chromophores, where the charge-transfer properties have been found to dictate the photo absorption efficiency and eventual device performance. Yet, as the chromophores are mostly bound onto the metal oxide surfaces by hydroxyl or carboxyl anchors, the impacts of the bonding interactions at the metal oxide-ligand interface on interfacial charge transfer have remained largely unexplored. Herein, acetylene derivatives are demonstrated as effective surface capping ligands for metal oxide nanoparticles, as exemplified with TiO2, RuO2, and ZnO. Experimental studies and first-principles calculations suggest the formation of M-O-C≡C- core-ligand linkages that lead to effective interfacial charge delocalization, in contrast to hopping/tunneling by the conventional M-O-CO- interfacial bonds in the carboxyl-capped counterparts. This leads to the generation of an interfacial state within the oxide bandgap and much enhanced sensitization of the nanoparticle photoluminescence emissions as well as photocatalytic activity, as manifested in the comparative studies with TiO2 nanoparticles functionalized with ethynylpyrene and pyrenecarboxylic acid. These results highlight the significance of the unique interfacial bonding chemistry by acetylene anchoring group in facilitating efficient charge transfer through the oxide-ligand interfacial linkage and hence the fundamental implication in their practical applications.

Graphene Composites with Cobalt Sulfide: Efficient Trifunctional Electrocatalysts for Oxygen Reversible Catalysis and Hydrogen Production in the Same Electrolyte.

Nitrogen and sulfur-codoped graphene composites with Co9 S8 (NS/rGO-Co) are synthesized by facile thermal annealing of graphene oxides with cobalt nitrate and thiourea in an ammonium atmosphere. Significantly, in 0.1 m KOH aqueous solution the best sample exhibits an oxygen evolution reaction (OER) activity that is superior to that of benchmark RuO2 catalysts, an oxygen reduction reaction (ORR) activity that is comparable to that of commercial Pt/C, and an overpotential of only -0.193 V to reach 10 mA cm-2 for hydrogen evolution reaction (HER). With this single catalyst for oxygen reversible electrocatalysis, a potential difference of only 0.700 V is observed in 0.1 m KOH solution between the half-wave potential in ORR and the potential to reach 10 mA cm-2 in OER; in addition, an overpotential of only 450 mV is needed to reach 10 mA cm-2 for full water splitting in the same electrolyte. The present trifunctional catalytic activities are markedly better than leading results reported in recent literature, where the remarkable trifunctional activity is attributed to the synergetic effects between N,S-codoped rGO, and Co9 S8 nanoparticles. These results highlight the significance of deliberate structural engineering in the preparation of multifunctional electrocatalysts for versatile electrochemical reactions.

Surface Functionalization of Metal Nanoparticles by Conjugated Metal-Ligand Interfacial Bonds: Impacts on Intraparticle Charge Transfer.

Noble metal nanoparticles represent a unique class of functional nanomaterials with physical and chemical properties that deviate markedly from those of their atomic and bulk forms. In order to stabilize the nanoparticles and further manipulate the materials properties, surface functionalization with organic molecules has been utilized as a powerful tool. Among those, mercapto derivatives have been used extensively as the ligands of choice for nanoparticle surface functionalization by taking advantage of the strong affinity of thiol moieties to transition metal surfaces forming (polar) metal-thiolate linkages. Yet, the nanoparticle material properties are generally discussed within the context of the two structural components, the metal cores and the organic capping layers, whereas the impacts of the metal-sulfur interfacial bonds are largely ignored because of the lack of interesting chemistry. In recent years, it has been found that metal nanoparticles may also be functionalized by stable metal-carbon (or even -nitrogen) covalent bonds. Because of the formation of dπ-pπ interactions between the transition-metal nanoparticles and terminal carbon moieties, the interfacial resistance at the metal-ligand interface is markedly reduced, leading to the emergence of unprecedented optical and electronic properties. In this Account, we summarize recent progress in the studies of metal nanoparticles functionalized by conjugated metal-ligand interfacial bonds that include metal-carbene (M═C) and metal-acetylide (M-C≡)/metal-vinylidene (M═C═C) bonds. Such interfacial bonds are readily formed by ligand self-assembly onto nanoparticle metal cores. The resulting nanoparticles exhibit apparent intraparticle charge delocalization between the particle-bound functional moieties, leading to the emergence of optical and electronic properties that are analogous to those of their dimeric counterparts, as manifested in spectroscopic and electrochemical measurements. This is first highlighted by ferrocene-functionalized nanoparticles that exhibit nanoparticle-mediated intervalence charge transfer (IVCT) among the particle-bound ferrocenyl moieties, as manifested in electrochemical and spectroscopic measurements. Such intraparticle charge delocalization has also been observed with other functional moieties such as pyrene and anthracene, where the photoluminescence emissions are consistent with those of their dimeric derivatives. Importantly, as such electronic communication occurs via a through-bond pathway, it may be readily manipulated by the valence states of the nanoparticle cores as well as specific binding of selective molecules/ions to the organic capping shells. These fundamental insights may be exploited for diverse applications, ranging from chemical sensing to (nano)electronics and fuel cell electrochemistry. Several examples are included, such as sensitive detection of nitroaromatic derivatives, metal cations, and fluoride anions by fluorophore-functionalized metal nanoparticles, fabrication of nanoparticle-bridged molecular dyads by, for instance, using nanoparticles cofunctionalized with 4-ethynyl-N,N-diphenyl-aniline (electron donor) and 9-vinylanthracene (electron acceptor), and enhanced electrocatalytic activity of acetylene derivatives-functionalized metal/alloy nanoparticles for oxygen reduction reaction by manipulation of the metal core electron density and hence interactions with reaction intermediates. We conclude this Account with a perspective where inspiration from conventional organometallic chemistry may be exploited for more complicated nanoparticle surface functionalization through the formation of diverse metal-nonmetal bonds. This is a unique platform for ready manipulation of nanoparticle properties and applications.

Nanoparticle-Mediated Intervalence Charge Transfer: Core-Size Effects.

Two types of platinum nanoparticles (NPs) functionalized with ethynylferrocene were prepared. The subnanometer-sized NPs (Pt10eFc) showed semiconductor-like characteristics with a bandgap of about 1.0 eV, and the other was metal-like with a core size of about 2 nm (Pt314eFc) and no significant bandgap. IR spectroscopic measurements showed a clear red-shift of the C≡C and ferrocenyl ring =C-H vibrational energies with increasing particle core size owing to enhanced intraparticle charge delocalization between the particle-bound ferrocenyl moieties. Electrochemical measurements showed two pairs of voltammetric peaks owing to intervalence charge transfer between the ferrocenyl groups on the nanoparticle surface, which was apparently weaker with Pt10 eFc than with Pt314 eFc. Significantly, the former might be markedly enhanced with UV photoirradiation owing to enhanced nanoparticle electronic conductivity, whereas no apparent effects were observed with the latter.

Hollow-Structured and Polyhedron-Shaped High Entropy Oxide toward Highly Active and Robust Oxygen Evolution Reaction in a Full pH Range.

High entropy metal oxides (HEO) are superior to many reactions involving multi-step elementary reactions. However, controlled synthesis of hollow-structured HEO catalysts, which offers large surface area and fast mass transfer kinetics, remains challenging and unexplored due to the complicated metal precursors. Herein, a metal organic framework-templated synthesis of hollow-structured and polyhedron-shaped HEO catalysts assembled with ultra-small nanoparticles, with up to ten metal elements, can be achieved, by taking advantage of the ion-exchange method. ZnFeNiCuCoRu-O HEO catalyst displays excellent activity and ultra-stability for oxygen evolution reaction in full pH range, with an overpotential of 170 mV at a current density of 10 mA cm-2 , a Tafel slope of 56 mV dec-1 , and a decay of activity by 7% in 30 h in alkaline medium, as well as a 12% and 8% decay in acidic and neutral medium, respectively. DFT calculation indicates that the energy barrier of the potential determining step on Ru-Fe bridge site is significantly lower than any other Ru-related bridge sites for the unique hollow structured HEO structures. This work highlights the importance of ion-exchange method in preparing highly stable and active hollow-structured HEOs catalysts toward highly efficient energy conversion and storage devices.

Octahedral Nanocrystals of Ru-Doped PtFeNiCuW/CNTs High-Entropy Alloy: High Performance towards pH-Universal Hydrogen Evolution Reaction.

Integrating high-entropy philosophy and nanocrystal-specific orientation into a single catalyst represents a promising strategy in the development of high-performance catalysts. Nonetheless, shape-controlled synthesis of high-entropy alloy (HEA) nanocrystals is a challenging task owing to the distinct redox potentials and growth dynamics of metal elements. Herein, a one-pot co-reduction method is developed to fabricate ruthenium (Ru)-doped PtFeNiCuW octahedral HEA nanocrystals onto carbon nanotubes (Ru-PtFeNiCuW/CNTs). It is demonstrated that Ru dopants and W(CO)6 promote the concurrent reduction and growth of other metal precursors to obtain higher yield and larger size of HEA nanocrystals, despite the low Ru content in Ru-PtFeNiCuW/CNTs. As an electrocatalyst towards hydrogen evolution reaction (HER), Ru-PtFeNiCuW/CNTs exhibits a low overpotentials of 9, 16 and 34 mV at a current density of 10 mA cm-2 and Tafel slope of 19.2, 27.9 and 23.1 mV dec-1 in acidic, alkaline and neutral electrolytes, respectively. As a cathodic catalyst, Ru-PtFeNiCuW/CNTs operates for up to 1500 and 1200 hours in acidic and alkaline electrolyte, respectively, at a current density of 50 mA cm-2 in a two-electrode system for full water splitting. Theoretical calculations reveal the accelerated kinetics of H2O dissociation on W sites and *H desorption on hollow Cu-Cu-Cu and Cu-Cu-Pt sites. This article is protected by copyright. All rights reserved.

Highly-dispersed nickel species on nitrogen-doped porous carbon: Significant local pH-buffering capacity and favorable CO desorption for efficient and robust electro-reduction of CO2.

Electrocatalytic reduction of CO2 (CO2RR) to value-added fuels and chemicals can potentially serve as a promising strategy to curb CO2 accumulation and carbon neutral cycle, but is still plagued by sluggish kinetics, poor selectivity and weak durability. Herein, we developed highly-dispersed nickel species on the nitrogen-doped carbon materials (Ni/NC) via the double solvent method (DSM), followed by the pyrolysis. The as-prepared Ni/NC possesses high CO2-to-CO selectivity of 93.2%∼98.6% at broad potential range (0.57 âˆ¼ 0.97 VRHE), decent jCO of 57.9 mAcm-2 at -1.07 VRHE, and significant robustness (retaining 96.3% of the initial faradaic efficiency for CO formation after 50 h electrolysis). As manifested by the rotating ring-disk electrode (RRDE) tests, the DSM-based Ni/NC possesses more significant pH-buffering capacity than Ni nanoparticles, thus promotes the CO2-to-CO. DFT calculations unveil that Ni/NC exhibits relatively lower d-band center, hence resulting in favorable desorption of CO from the catalyst surface that intrinsically boost the CO2-to-CO compared with the nanoparticle catalyst. These results suggest that the DSM-derived Ni/NC catalysts is a promising candidate towards large-scale application of CO2-to-CO.

PEDOT-intercalated NH4V3O8 nanobelts as high-performance cathode materials for potassium ion batteries.

Potassium ion batteries (PIBs) have great potential to replace lithium ion batteries (LIBs) for large-scale energy storage applications because of the low cost and earth abundance of potassium resources. However, it is critically challenging to exploit an appropriate cathode material to accommodate the large size of K+. Herein, a conducting polymer (PEDOT) intercalation method is utilized to tailor the interlayer spacing of NH4V3O8 nanobelts from 7.8 Å to 10.8 Å, and afford rich oxygen vacancies inside the vanadate, thus enhancing its electronic conductivity and accelerating the K+ insertion/extraction kinetics. Benefiting from these features, PEDOT-intercalated NH4V3O8 (PNVO) nanobelts deliver an improved capacity of 87 mA h g-1 at 20 mA g-1, high rate capability of 51 mA h g-1 at 500 mA g-1, and a stable cycle life (capacity retention of 92.5 % after 100 cycles at 50 mA g-1). Even cycled at 200 mA g-1, PNVO nanobelts feature a long cycle life over 300 cycles with a capacity retention of 71.7 %. This work is of great significance for exploitation of PIBs cathode with improved electrochemical performance through pre-intercalation and defect engineering.

Covalent Functionalization of Black Phosphorus Nanosheets with Dichlorocarbenes for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

Two-dimensional black phosphorus (BP) has emerged as a perspective material for various micro- and opto-electronic, energy, catalytic, and biomedical applications. Chemical functionalization of black phosphorus nanosheets (BPNS) is an important pathway for the preparation of materials with improved ambient stability and enhanced physical properties. Currently, the covalent functionalization of BPNS with highly reactive intermediates, such as carbon-free radicals or nitrenes, has been widely implemented to modify the material's surface. However, it should be noted that this field requires more in-depth research and new developments. Herein, we report for the first time the covalent carbene functionalization of BPNS using dichlorocarbene as a functionalizing agent. The P-C bond formation in the obtained material (BP-CCl2) has been confirmed by Raman, solid-state 31P NMR, IR, and X-ray photoelectron spectroscopy methods. The BP-CCl2 nanosheets exhibit an enhanced electrocatalytic hydrogen evolution reaction (HER) performance with an overpotential of 442 mV at -1 mA cm-2 and a Tafel slope of 120 mV dec-1, outperforming the pristine BPNS.

Alkyne-functionalized ruthenium nanoparticles: ruthenium-vinylidene bonds at the metal-ligand interface.

Stable ruthenium nanoparticles were prepared by the self-assembly of 1-dodecyne onto the "bare" Ru colloid surface. The formation of a Ru-vinylidene (Ru═C═CH-R) interfacial bonding linkage was confirmed by the specific reactivity of the nanoparticles with imine derivatives to form a heterocyclic complex at the metal-ligand interface, as manifested in (1)H and (13)C NMR, photoluminescence, and electrochemical measurements in which a ferrocenyl imine was used as the labeling probe. Notably, the resulting nanoparticles could also undergo olefin metathesis reactions with vinyl-terminated molecules, as exemplified by the functionalization of the nanoparticles with 1-vinylpyrene. In sharp contrast, no reactvity was observed with 1-dodecynide-stabilized ruthenium nanoparticles with either imine or vinyl derivatives, indicating that these (deprotonated) nanoparticles were stabilized instead by the formation of a Ru-C≡ dπ bond at the metal-ligand interface.

Manipulation of intraparticle charge delocalization by selective complexation of transition-metal ions with histidine moieties.

Ruthenium nanoparticles were cofunctionalized with pyrene and histidine moieties through Ru═carbene π bonds. The selective complexation of the histidine moiety with transition-metal ions led to a marked diminishment of the emission peak at 490 nm which arose from the nanoparticle-bridged pyrene moieties that behaved analogously to pyrene dimers with a conjugated spacer. This is accounted for by the polarization of the core electrons by the added positive charge that impacted the intraparticle charge delocalization between the particle-bound pyrene moieties. This electronic interaction was likely facilitated by the π interactions between the metal ions and the imidazole ring as well as by the conjugated molecular backbone that linked the imidazole ring to the nanoparticle cores. Within the present experimental context, of all the metal ions tested, the impacts were much more drastic with Pb(2+), Co(2+), and Hg(2+) than with Li(+), K(+), Rb(+), Mg(2+), Ca(2+), and Zn(2+) ions, with the most sensitive variation observed with Pb(2+). This is ascribed to the enhanced π interactions of the histidine moiety with the Pb(2+), Co(2+), and Hg(2+) ions because of their capability of donating d electrons, a behavior consistent with prior studies based on conventional histidine-metal ion complexes.

Butylphenyl-functionalized Pt nanoparticles as CO-resistant electrocatalysts for formic acid oxidation.

Butylphenyl-functionalized Pt nanoparticles (Pt-BP) with an average core diameter of 2.93 ± 0.49 nm were synthesized by the co-reduction of butylphenyl diazonium salt and H(2)PtCl(4). Cyclic voltammetric studies of the Pt-BP nanoparticles showed a much less pronounced hysteresis between the oxidation currents of formic acid in the forward and reverse scans, as compared to that on naked Pt surfaces. Electrochemical in situ FTIR studies confirmed that no adsorbed CO, a poisoning intermediate, was generated on the Pt-BP nanoparticle surface. These results suggest that functionalization of the Pt nanoparticles by butylphenyl fragments effectively blocked the CO poisoning pathway, most probably through third-body effects, and hence led to an apparent improvement of the electrocatalytic activity in formic acid oxidation.

Promoting biomass electrooxidation via modulating proton and oxygen anion deintercalation in hydroxide.

The redox center of transition metal oxides and hydroxides is generally considered to be the metal site. Interestingly, proton and oxygen in the lattice recently are found to be actively involved in the catalytic reactions, and critically determine the reactivity. Herein, taking glycerol electrooxidation reaction as the model reaction, we reveal systematically the impact of proton and oxygen anion (de)intercalation processes on the elementary steps. Combining density functional theory calculations and advanced spectroscopy techniques, we find that doping Co into Ni-hydroxide promotes the deintercalation of proton and oxygen anion from the catalyst surface. The oxygen vacancies formed in NiCo hydroxide during glycerol electrooxidation reaction increase d-band filling on Co sites, facilitating the charge transfer from catalyst surface to cleaved molecules during the 2nd C-C bond cleavage. Consequently, NiCo hydroxide exhibits enhanced glycerol electrooxidation activity, with a current density of 100 mA/cm2 at 1.35 V and a formate selectivity of 94.3%.

Electrochemical CO2 reduction catalyzed by atomically precise alkynyl-protected Au7Ag8, Ag9Cu6, and Au2Ag8Cu5 nanoclusters: probing the effect of multi-metal core on selectivity.

Doping metal nanoclusters (NCs) with another metal usually leads to superior catalytic performance toward CO2 reduction reaction (CO2RR), yet elucidating the metal core effect is still challenging. Herein, we report the systematic study of atomically precise alkynyl-protected Au7Ag8, Ag9Cu6, and Au2Ag8Cu5 NCs toward CO2RR. Au2Ag8Cu5 prepared by a site-specific metal exchange approach from Ag9Cu6 is the first case of trimetallic superatom with full-alkynyl protection. The three M15 clusters exhibited drastically different CO2RR performance. Specifically, Au7Ag8 demonstrated high selectivity for CO formation in a wide voltage range (98.1% faradaic efficiency, FE, at -0.49 V and 89.0% FE at -1.20 V vs. RHE), while formation of formate becomes significant for Ag9Cu6 and Au2Ag8Cu5 at more negative potentials. DFT calculations demonstrated that the exposed, undercoordinated metal atoms are the active sites and the hydride transfer as well as HCOO* stabilization on the Cu-Ag site plays a critical role in the formate formation. Our work shows that, tuning the metal centers of the ultrasmall metal NCs via metal exchange is very useful to probe the structure-selectivity relationships for CO2RR.

Intraparticle charge delocalization of carbene-functionalized ruthenium nanoparticles manipulated by selective ion binding.

Olefin metathesis reactions of carbene-stabilized ruthenium nanoparticles were exploited for the incorporation of multiple functional moieties onto the nanoparticle surface. When the nanoparticles were cofunctionalized with 4-vinylbenzo-18-crown-6 and 1-vinylpyrene, the resulting particles exhibited fluorescence characteristics that were consistent with dimeric pyrene with a conjugated chemical bridge, with three peaks observed in the emission spectra at 391, 410, and 485 nm. The behaviors were ascribed to intraparticle charge delocalization between the pyrene moieties afforded by the conjugated Ru═carbene interfacial linkages. Notably, upon the binding of metal ions in the crown ether cavity, the emission intensity of the nanoparticle fluorescence was found to diminish at 485 nm and concurrently increase at 391 and 410 nm rather markedly, with the most significant effects observed with K(+). This was accounted for by the selective binding of 18-crown-6 to potassium ions, where the positively charged ions led to the polarization of the nanoparticle core electrons that was facililated by the conjugated linkage to the metal surface and hence impeded intraparticle charge delocalization. Control experiments with a pyrene-crown ether conjugate (2) and with ruthenium nanoparticles cofunctionalized with 4-vinylbenzo-18-crown-6 and 1-allylpyrene suggested that the through-bond pathway played a predominant role in the manipulation of intraparticle electronic communication whereas the contributions from simple electrostatic interactions (i.e., through-space pathway) were minimal.

Nitrene-functionalized ruthenium nanoparticles: Spectral evidence for the conjugated ruthenium-nitrene π bonds and the impact on the catalytic activity.

In this manuscript, ruthenium (Ru) nanoparticles functionalized with nitrene ligands through the ruthenium-nitrene (RuN) π bonds are explored. By synthesizing the nitrene ligands with and without 15N-labelling, RuN π bonds on Ru nanoparticles are evidenced by experimental and theoretically calculated FTIR spectra. The coordination of nitrene ligands on Ru nanoparticles surface, the interfacial charge delocalization and the impact of nitrene ligands on the catalytic performance of Ru nanoparticles are further characterized by magic-angle spinning solid-state carbon nuclear magnetic resonance spectroscopy (13C NMR) of 13CO-adsorbed Ru nanoparticles, photoluminescence and the hydrogenation of styrene.