Facet-Defined Dilute Metal Alloy Nanorods for Efficient Electroreduction of CO2 to n-Propanol.

Electroreduction of CO2 into liquid fuels is a compelling strategy for storing intermittent renewable energy. Here, we introduce a family of facet-defined dilute copper alloy nanocrystals as catalysts to improve the electrosynthesis of n-propanol from CO2 and H2O. We show that substituting a dilute amount of weak-CO-binding metals into the Cu(100) surface improves CO2-to-n-propanol activity and selectivity by modifying the electronic structure of catalysts to facilitate C1-C2 coupling while preserving the (100)-like 4-fold Cu ensembles which favor C1-C1 coupling. With the Au0.02Cu0.98 champion catalyst, we achieve an n-propanol Faradaic efficiency of 18.2 ± 0.3% at a low potential of -0.41 V versus the reversible hydrogen electrode and a peak production rate of 16.6 mA·cm-2. This study demonstrates that shape-controlled dilute-metal-alloy nanocrystals represent a new frontier in electrocatalyst design, and precise control of the host and minority metal distributions is crucial for elucidating structure-composition-property relationships and attaining superior catalytic performance.

A Spectroscopically Observed Iron Nitrosyl Intermediate in the Reduction of Nitrate by a Surface-Conjugated Electrocatalyst.

We report an iron-based graphite-conjugated electrocatalyst (GCC-FeDIM) that combines the well-defined nature of homogeneous molecular electrocatalysts with the robustness of a heterogeneous electrode. A suite of spectroscopic methods, supported by the results of DFT calculations, reveals that the electrode surface is functionalized by high spin (S = 5/2) Fe(III) ions in an FeN4Cl2 coordination environment. The chloride ions are hydrolyzed in aqueous solution, with the resulting cyclic voltammogram revealing a Gaussian-shaped wave assigned to 1H+/1e- reduction of surface Fe(III)-OH surface. A catalytic wave is observed in the presence of NO3-, with an onset potential of -1.1 V vs SCE. At pH 6.0, GCC-FeDIM rapidly reduces NO3- to ammonium and nitrite with 88 and 6% Faradaic efficiency, respectively. Mechanistic studies, including in situ X-ray absorption spectroscopy, suggest that electrocatalytic NO3- reduction involves an iron nitrosyl intermediate. The Fe-N bond length (1.65 Å) is similar to that observed in {Fe(NO)}6 complexes, which is supported by the results of DFT calculations.

Graphite Conjugation of a Macrocyclic Cobalt Complex Enhances Nitrite Electroreduction to Ammonia.

This work reports on the generation of a graphite-conjugated diimine macrocyclic Co catalyst (GCC-CoDIM) that is assembled at o-quinone edge defects on graphitic carbon electrodes. X-ray photoelectron spectroscopy and X-ray absorption spectroscopy confirm the existence of a new Co surface species with a coordination environment that is the same as that of the molecular analogue, [Co(DIM)Br2]+. GCC-CoDIM selectively reduces nitrite to ammonium with quantitative Faradaic efficiency and at a rate that approaches enzymatic catalysis. Preliminary mechanistic investigations suggest that the increased rate is accompanied by a change in mechanism from the molecular analogue. These results provide a template for creating macrocycle-based electrocatalysts based on first-row transition metals conjugated to an extreme redox-active ligand.

Broadband Tunable Mid-infrared Plasmon Resonances in Cadmium Oxide Nanocrystals Induced by Size-Dependent Nonstoichiometry.

A central theme of nanocrystal (NC) research involves synthesis of dimension-controlled NCs and studyof size-dependent scaling laws governing their optical, electrical, magnetic, and thermodynamic properties. Here, we describe the synthesis of monodisperse CdO NCs that exhibit high quality-factor (up to 5.5) mid-infrared (MIR) localized surface plasmon resonances (LSPR) and elucidate the inverse scaling relationship between carrier concentration and NC size. The LSPR wavelength is readily tunable between 2.4 and ∼6.0 µm by controlling the size of CdO NCs. Structural and spectroscopic characterization provide strong evidence that free electrons primarily originate from self-doping due to NC surface-induced nonstoichiometry. The ability to probe and to control NC stoichiometry and intrinsic defects will pave the way toward predictive synthesis of doped NCs with desirable LSPR characteristics.

Strong π-Backbonding Enables Record Magnetic Exchange Coupling Through Cyanide.

The paramagnetic cyano-bridged complex PhB(tBuIm)3Fe-NC-Mo(NtBuAr)3 (Ar = 3,5-Me2C6H3) is readily assembled from a new four-coordinate, high-spin (S = 2) iron(II) monocyanide complex and the three-coordinate molybdenum(III) complex Mo(NtBuAr)3. X-ray diffraction and IR spectroscopy reveal that delocalization of unpaired electron density into the cyanide π* orbitals leads to a reduction of the C-N bond order. Direct current (dc) magnetic susceptibility measurements, supported by electronic structure calculations, demonstrate the presence of strong antiferromagnetic exchange between spin centers, with a coupling constant of J = -122(2) cm-1. To our knowledge, this value represents the strongest magnetic exchange coupling ever to be observed through cyanide. These results demonstrate the ability of low-coordinate metal fragments to engender extremely strong magnetic exchange coupling through cyanide by virtue of significant π-backbonding into the cyanide ligand.

Effect of Stacking Interactions on the Translation of Structurally Related Bis(thiosemicarbazonato)nickel(II) HER Catalysts to Modified Electrode Surfaces.

A series of crystalline nickel(II) complexes (1-3) based on inexpensive bis(thiosemicarbazone) ligands diacetylbis(4-methyl-3-thiosemicarbazone) (H2ATSM), diacetylbis(4,4-dimethyl-3-thiosemicarbazone) (H2ATSDM), and diacetylbis[4-(2,2,2-trifluoroethyl)-3-thiosemicarbazone] (H2ATSM-F6) were synthesized and characterized by single-crystal X-ray diffraction and NMR, UV-visible, and Fourier transform infrared spectroscopies. Modified electrodes GC-1-GC-3 were prepared with films of 1-3 deposited on glassy carbon and evaluated as potential hydrogen evolution reaction (HER) catalysts. HER studies in 0.5 M aqueous H2SO4 (10 mA cm-2) revealed dramatic shifts in the overpotential from 0.740 to 0.450 V after extended cycling for 1 and 2. The charge-transfer resistances for GC-1-GC-3 were determined to be 270, 160, and 630 Ω, respectively. Characterization of the modified surfaces for GC-1 and GC-2 by scanning electron microscopy and Raman spectroscopy revealed similar crystalline coatings before HER that changed to surface-modified crystallites after conditioning. The surface of GC-3 had an initial glasslike appearance before HER that delaminated after HER. The differences in the surface morphology and the effect of conditioning are correlated with crystal-packing effects. Complexes 1 and 2 pack as columns of interacting complexes in the crystallographic a direction with short interplanar spacings between 3.37 and 3.54 Å. Complex 3 packs as columns of isolated molecules in the crystallographic b direction with long-range interplanar spacings of 9.40 Å.

Utilizing Charge Effects and Minimizing Intramolecular Proton Rearrangement to Improve the Overpotential of a Thiosemicarbazonato Zinc HER Catalyst.

The zinc(II) complex of diacetyl-2-(4-methyl-3-thiosemicarbazone)-3-(2-hydrazonepyridine), ZnL1 (1), was prepared and evaluated as a precatalyst for the hydrogen evolution reaction (HER) under homogeneous conditions in acetonitrile. Complex 1 is protonated on the noncoordinating nitrogen of the hydrazonepyridine moiety to yield the active catalyst Zn(HL1)OAc (2) upon addition of acetic acid. Addition of methyl iodide to 1 yields the corresponding methylated derivative ZnL2I (3). In solution, partial dissociation of the coordinated iodide yields the cationic derivative 3'. Complexes 1-3 were characterized by 1H NMR, FT-IR, and UV-visible spectroscopies. The solid-state structures of 2 and 3 were determined by single crystal X-ray diffraction. HER studies conducted in acetonitrile with acetic acid as the proton source yield a turnover frequency (TOF) of 7700 s-1 for solutions of 1 at an overpotential of 1.27 V and a TOF of 6700 s-1 for solutions of 3 at an overpotential of 0.56 V. For both complexes, the required potential for catalysis, Ecat/2, is larger than the thermodynamic reduction potential, E1/2, indicative of a kinetic barrier attributed to intramolecular proton rearrangement. The effect is larger for solutions of 1 (+440 mV) than for solutions of 3 (+160 mV). Controlled potential coulometry studies were used to determine faradaic efficiencies of 71 and 89% for solutions of 1 and 3, respectively. For both catalysts, extensive cycling of potential under catalytic conditions results in the deposition of a film on the glassy carbon electrode surface that is active as an HER catalyst. Analysis of the film of 3 by X-ray photoelectron spectroscopy indicates the complex remains intact upon deposition. A proposed ligand-centered HER mechanism with 1 as a precatalyst to 2 is supported computationally using density functional theory (DFT). All catalytic intermediates in the mechanism were structurally and energetically characterized with the DFT/B3LYP/6-311g(d,p) in solution phase using a polarizable continuum model (PCM). The thermodynamic feasibility of the mechanism is supported by calculation of equilibrium constants or reduction potentials for each proposed step.

Seeking Redox Activity in a Tetrazinyl Pincer Ligand: Installing Zerovalent Cr and Mo.

Reaction of the readily reduced pincer ligand bis-tetrazinylpyridine, btzp, with the zerovalent metal source M(CO)3(MeCN)3 yields M(btzp)2 for M = Cr, Mo. These diamagnetic molecules show intrapincer bond lengths consistent with major charge transfer from metal to ligand, a result which is further supported by X-ray photoelectron spectroscopy. These molecules show up to five reversible outer-sphere electron transfers by cyclic voltammetry. The electronic structure of neutral M(btzp)2 is analyzed by DFT and CASSCF calculations, which reveal the degree of back-donation from the metal into pincer π* orbitals and also subtle differences in metal-ligand interaction for Mo vs Cr. Near-IR absorptions exhibited by both M(btzp)2 species originate from charge transfer among differently reduced tetrazine rings, which thus further support pincer reduction in these species.

A Multifunctional Pincer Ligand Supports Unsaturated Cobalt: Five Functionalities in One Pincer.

A pyridyl pincer ligand was developed to incorporate steric bulk, through a PtBu2 arm, and proton responsivity, through a pyrazole pincer ligand arm, together with reactivity at benzylic hydrogen and redox activity within a 1,4 diazabutadiene moiety. Binding it to CoCl2 yielded square-pyramidal [(PNNH)CoCl2 ], which was deprotonated by Li[N(SiMe3 )2 ] to form [{Li(THF)2 PNN}CoCl2 ]. Reduction of this LiCl adduct with KC8 under CO atmosphere led to formation of CoI mono- and dicarbonyl complexes, which can be protonated but also further deprotonated at the benzylic CH group to give a dearomatized pyridyl group. The ligand was characterized in its neutral, monoanionic, and dianionic forms, and the anions were shown to exist as intimate ion pairs with Li+ bound to pyrazolate N and chloride bound to Lewis acidic cobalt. X-ray photoelectron spectroscopy was used to assay both Li content and cobalt oxidation states. The general character of binding of LiCl to a metal complex acidic at metal and nucleophilic at ligand (pyrazolate Nß) is discussed, as are potential catalytic applications of the concept.

Oriented Attachment Is a Major Control Mechanism To Form Nail-like Mn-Doped ZnO Nanocrystals.

Here, we present a controlled synthesis of Mn-doped ZnO nanoparticles (NPs) with predominantly nail-like shapes, whose formation occurs via tip-to-base-oriented attachment of initially formed nanopyramids, followed by leveling of sharp edges that lead to smooth single-crystalline "nails". This shape is prevalent in noncoordinating solvents such as octadecene and octadecane. Yet, the double bond in the former promotes oriented attachment. By contrast, Mn-doped ZnO NP synthesis in a weakly coordinating solvent, benzyl ether, results in dendritic structures because of random attachment of initial NPs. Mn-doped ZnO NPs possess a hexagonal wurtzite structure, and in the majority of cases, the NP surface is enriched with Mn, indicating a migration of Mn2+ ions to the NP surface during the NP formation. When the NP formation is carried out without the addition of octadecyl alcohol, which serves as a surfactant and a reaction initiator, large, concave pyramid dimers are formed whose attachment takes place via basal planes. UV-vis and photoluminescence spectra of these NPs confirm the utility of controlling the NP shape to tune electro-optical properties.

Evidence for Quinone Redox Chemistry Mediating Daytime and Nighttime NO2-to-HONO Conversion on Soil Surfaces.

Humic acid (HA) is thought to promote NO2 conversion to nitrous acid (HONO) on soil surfaces during the day. However, it has proven difficult to identify the reactive sites in natural HA substrates. The mechanism of NO2 reduction on soil surrogates composed of HA and clay minerals was studied by use of a coated-wall flow reactor and cavity-enhanced spectroscopy. Conversion of NO2 to HONO in the dark was found to be significant and correlated to the abundance of C-O moieties in HA determined from the X-ray photoelectron spectra of the C 1s region. Twice as much HONO was formed when NO2 reacted with HA that was photoreduced by irradiation with UV-visible light compared to the dark reaction; photochemical reactivity was correlated to the abundance of C═O moieties rather than C-O groups. Bulk electrolysis was used to generate HA in a defined reduction state. Electrochemically reduced HA enhanced NO2-to-HONO conversion by a factor of 2 relative to non-reduced HA. Our findings suggest that hydroquinones and benzoquinones, which are interchangeable via redox equilibria, contribute to both thermal and photochemical HONO formation. This conclusion is supported by experiments that studied NO2 reactivity on mineral surfaces coated with the model quinone, juglone. Results provide further evidence that redox-active sites on soil surfaces drive ground-level NO2-to-nitrite conversion in the atmospheric boundary layer throughout the day, while amphoteric mineral surfaces promote the release of nitrite formed as gaseous HONO.

pH-Induced Surface Modification of Atomically Precise Silver Nanoclusters: An Approach for Tunable Optical and Electronic Properties.

Noble metal nanoclusters (NCs) play a pivotal role in bridging the gap between molecules and quantum dots. Fundamental understanding of the evolution of the structural, optical, and electronic properties of these materials in various environments is of paramount importance for many applications. Using state-of-the-art spectroscopy, we provide the first decisive experimental evidence that the structural, electronic, and optical properties of Ag44(MNBA)30 NCs can now be tailored by controlling the chemical environment. Infrared and photoelectron spectroscopies clearly indicate that there is a dimerization between two adjacent ligands capping the NCs that takes place upon lowering the pH from 13 to 7.

The Role of Iron-Bearing Minerals in NO2 to HONO Conversion on Soil Surfaces.

Nitrous acid (HONO) accumulates in the nocturnal boundary layer where it is an important source of daytime hydroxyl radicals. Although there is clear evidence for the involvement of heterogeneous reactions of NO2 on surfaces as a source of HONO, mechanisms remain poorly understood. We used coated-wall flow tube measurements of NO2 reactivity on environmentally relevant surfaces (Fe (hydr)oxides, clay minerals, and soil from Arizona and the Saharan Desert) and detailed mineralogical characterization of substrates to show that reduction of NO2 by Fe-bearing minerals in soil can be a more important source of HONO than the putative NO2 hydrolysis mechanism. The magnitude of NO2-to-HONO conversion depends on the amount of Fe(2+) present in substrates and soil surface acidity. Studies examining the dependence of HONO flux on substrate pH revealed that HONO is formed at soil pH < 5 from the reaction between NO2 and Fe(2+)(aq) present in thin films of water coating the surface, whereas in the range of pH 5-8 HONO stems from reaction of NO2 with structural iron or surface complexed Fe(2+) followed by protonation of nitrite via surface Fe-OH2(+) groups. Reduction of NO2 on ubiquitous Fe-bearing minerals in soil may explain HONO accumulation in the nocturnal boundary layer and the enhanced [HONO]/[NO2] ratios observed during dust storms in urban areas.

Tailoring ruthenium exposure to enhance the performance of fcc platinum@ruthenium core-shell electrocatalysts in the oxygen evolution reaction.

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ∼2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Organotrisulfide: A High Capacity Cathode Material for Rechargeable Lithium Batteries.

An organotrisulfide (RSSSR, R is an organic group) has three sulfur atoms which could be involved in multi-electron reduction reactions; therefore it is a promising electrode material for batteries. Herein, we use dimethyl trisulfide (DMTS) as a model compound to study its redox reactions in rechargeable lithium batteries. With the aid of XRD, XPS, and GC-MS analysis, we confirm DMTS could undergo almost a 4 e(-) reduction process in a complete discharge to 1.0 V. The discharge products are primarily LiSCH3 and Li2 S. The lithium cell with DMTS catholyte delivers an initial specific capacity of 720 mAh g(-1) DMTS and retains 82 % of the capacity over 50 cycles at C/10 rate. When the electrolyte/DMTS ratio is 3:1 mL g(-1) , the reversible specific energy for the cell including electrolyte can be 229 Wh kg(-1) . This study shows organotrisulfide is a promising high-capacity cathode material for high-energy rechargeable lithium batteries.

Partial nitrogen atom transfer: a new synthetic tool to design single-molecule magnets.

Incomplete nitrogen atom transfer from the iron(IV) nitride complex PhB(MesIm)3Fe≡N to the vanadium(III) complex V(Mes)3(THF) quantitatively provides the bimetallic complex PhB(MesIm)3Fe-N═V(Mes)3. Structural and spectroscopic characterizations reveal that the nitride ligand forms a linear bridge between V(V) and high-spin Fe(II) metal ions, confirming that atom transfer is accompanied by electron transfer. In the presence of an applied dc field, the complex displays slow relaxation of the magnetization, revealing its single-molecule magnet properties with an estimation of the energy barrier at about 10 K. This complex establishes a synthetic principle for the assembly of paramagnetic complexes bridged by nitride ligands.

Shaping the synthesis and assembly of symmetrically stellated Au/Pd nanocrystals with aromatic additives.

Au/Pd octopods were synthesized with enhanced sample homogeneity through the use of aromatic additives. This increase in sample monodispersity facilitates large-area periodic assembly of stellated metal nanostructures for the first time. The aromatic additives were also found to influence the structures of the stellated nanocrystals with subtle shape modifications observed that can alter the packing arrangement of the Au/Pd octopods. These results indicate the possibility of tailored assembly of stellated nanostructures, which would be useful for optical applications that require strong and predictable coupling between plasmonic building blocks.

Chemical implications of incompatible ligand versus metal coordination geometry preferences.

Binding an electron deficient pincer ligand which strongly dictates planar, mer stereochemistry, to a metal which prefers tetrahedral structure, e.g., d(10) CuCl, is explored for possible intramolecular redox chemistry. Experiment shows that the pincer ligand 2,2'-bis-tetrazinyl pyridine, btzp, forms a complex (btzp)CuCl which is a chloride-bridged polymer in the solid state, hence with 20 valence electrons around copper. DFT calculations show that even the monomer has nonplanar copper with the tetrazinyl nitrogen lone pairs somewhat misdirected away from copper, with long Cu/N bonds, in a singlet ground state; 13.9 kcal/mol less stable is a triplet, whose electronic structure shows one electron from the ground state Cu(I) has been transferred to a pincer π* orbital. Outer sphere electron transfer to (btzp)CuCl yields (btzp)Cu where the added electron has gone into the pincer, to leave a ligand-centered radical, characterized by EPR, chemical reactivity, and X-ray photoelectron spectroscopy.

Ligand-stabilized and atomically precise gold nanocluster catalysis: a case study for correlating fundamental electronic properties with catalysis.

We present results from our investigations into correlating the styrene-oxidation catalysis of atomically precise mixed-ligand biicosahedral-structure [Au25(PPh3)10(SC12H25)5Cl2](2+) (Au25-bi) and thiol-stabilized icosahedral core-shell-structure [Au25(SCH2CH2Ph)18](-) (Au25-i) clusters with their electronic and atomic structure by using a combination of synchrotron radiation-based X-ray absorption fine-structure spectroscopy (XAFS) and ultraviolet photoemission spectroscopy (UPS). Compared to bulk Au, XAFS revealed low Au-Au coordination, Au-Au bond contraction and higher d-band vacancies in both the ligand-stabilized Au clusters. The ligands were found not only to act as colloidal stabilizers, but also as d-band electron acceptor for Au atoms. Au25-bi clusters have a higher first-shell Au coordination number than Au25-i, whereas Au25-bi and Au25-i clusters have the same number of Au atoms. The UPS revealed a trend of narrower d-band width, with apparent d-band spin-orbit splitting and higher binding energy of d-band center position for Au25-bi and Au25-i. We propose that the differences in their d-band unoccupied state population are likely to be responsible for differences in their catalytic activity and selectivity. The findings reported herein help to understand the catalysis of atomically precise ligand-stabilized metal clusters by correlating their atomic or electronic properties with catalytic activity.

A bioinspired cobalt catalyst based on a tripodal imidazole/pyridine platform capable of water reduction and oxidation.

The prototypical drug carrier [CoII(L1)Cl]PF6 (1), where L1 is a tripodal amine bound to pyridine and methyl-imidazoles, had its electrocatalytic water splitting activity studied under different pH conditions. This species contains a high-spin 3d7 CoII metal center, and is capable of generating both H2 from water reduction and O2 from water oxidation. Turnover numbers reach 390 after 3 h for water reduction. Initial water oxidation activity is molecular, with TONs of 71 at pH 7 and 103 at pH 11.5. The results reveal that species 1 can undergo several redox transformations, including reduction to the 3d8 CoI species that precedes a LS3d6 hydride for water reduction, as well as nominal CoIVO and CoIII-OOH species required for water oxidation. Post-catalytic analyses confirm the molecular nature of reduction and support initial molecular activity for oxidation.