Tailoring the aluminum nanocrystal surface oxide for all-aluminum-based antenna-reactor plasmonic photocatalysts.

Aluminum nanocrystals (AlNCs) are of increasing interest as sustainable, earth-abundant nanoparticles for visible wavelength plasmonics and as versatile nanoantennas for energy-efficient plasmonic photocatalysis. Here, we show that annealing AlNCs under various gases and thermal conditions induces substantial, systematic changes in their surface oxide, modifying crystalline phase, surface morphology, density, and defect type and concentration. Tailoring the surface oxide properties enables AlNCs to function as all-aluminum-based antenna-reactor plasmonic photocatalysts, with the modified surface oxides providing varying reactivities and selectivities for several chemical reactions.

Molar excess of coordinating N-heterocyclic carbene ligands triggers kinetic digestion of gold nanocrystals.

There has been much interest in evaluating the strength of the coordination interactions between N-heterocyclic carbene (NHC) molecules and transition metal ions, nanocolloids and surfaces. We implement a top-down core digestion test of Au nanoparticles (AuNPs) triggered by incubation with a large molar excess of poly(ethylene glycol)-appended NHC molecules, where kinetic dislodging of surface atoms and formation of NHC-Au complexes progressively take place. We characterize the structure and chemical nature of the generated PEG-NHC-Au complexes using 1D and 2D 1H-13C NMR spectroscopy, supplemented with matrix assisted laser desorption/ionization mass spectrometry, and transmission electron microscopy. We further apply the same test using thiol-modified molecules and find that though etching can be measured the kinetics are substantially slower. We discuss our findings within the classic digestion of transition metal ores and colloids induced by interactions with sodium cyanide, which provides an insight into the strength of coordination between the strong σ-donating (soft Lewis base) NHC and Au surfaces (having a soft Lewis acid character), as compared to gold-to-gold covalent binding.

Metal Flux Growth of Lanthanide Carbide Hydrides Using Anthracene.

Reactions of anthracene in Ln/T eutectic mixtures (Ln = La, Yb; T = Ni, Cu) have produced crystals of new complex lanthanide carbide hydride phases. The thermal decomposition of anthracene provides a source of both carbon and hydrogen. LaCHx forms in space group Pnma with unit cell parameters a = 7.2736(4) Å, b = 3.7218(2) Å, and c = 13.0727(7) Å. Yb2CHx forms in space group P-3m1 with unit cell parameters a = 3.5659(4) Å and c = 5.8000(8) Å, with a structure related to that of Ho2CF2. The presence of hydride in interstitial sites is supported by the formation of different compounds in the absence of hydrogen and by comparison to known hydride structures. 1H nuclear magnetic resonance (NMR) spectra collected on LaCHx show two unique hydride resonances, in agreement with the two available interstitial sites. Density of states calculations show that filling the tetrahedral sites in LaCHx with hydrogen increases metallic behavior, while adding hydrogen into the tetrahedral sites in Yb2CHx induces the formation of a band gap.

Mechanistic insight into CdSe nanoplatelet-sensitized upconversion: size and stacking induced effects.

CdSe nanoplatelets (NPLs) have been reported as triplet sensitizers for photon upconversion (UC). However, their UC quantum yields lag behind more conventional systems. Here, we take advantage of their one-dimensional quantum confinement to decouple effects caused by the energetic driving force and lateral size. A surprising anti-correlation between the power threshold Ith and the UC quantum yield based on the NPL size is found. We attribute this result to two distinct triplet-triplet annihilation mechanisms based on the NPL lateral dimension and degree of NPL stacking-mediated either by molecular diffusion or triplet energy diffusion.

LiMo8O10: Polar Crystal Structure with Infinite Edge-Sharing Molybdenum Octahedra.

Polycrystalline LiMo8O10 was prepared in a sealed Mo crucible at 1380 °C for 48 h using the conventional high-temperature solid-state method. The polar tetragonal crystal structure (space group I41md) is confirmed based on the Rietveld refinement of powder neutron diffraction and 7Li/6Li solid-state NMR. The crystal structure features infinite chains of Mo4O5 (i.e., Mo2Mo4/2O6/2O6/3) as a repeat unit containing edge-sharing Mo6 octahedra with strong Mo-Mo metal bonding along the chain. X-ray absorption near-edge spectroscopy of the Mo-L3 edge is consistent with the formal Mo valence/configuration. Magnetic measurements reveal that LiMo8O10 is paramagnetic down to 1.8 K. Temperature-dependent resistivity [ρ(T)] measurement indicates a semiconducting behavior that can be fitted with Mott's variable range hopping conduction mechanism in the temperature range of 215 and 45 K. The ρ(T) curve exhibits an exponential increase below 5 K with a large ratio of ρ1.8/ρ300 = 435. LiMo8O10 shows a negative field-dependent magnetoresistance between 2 and 25 K. Heat capacity measurement fitted with the modified Debye model yields the Debye temperature of 365 K.

Luminescent Quantum Dots Stabilized by N-Heterocyclic Carbene Polymer Ligands.

We have tested the ability of N-heterocyclic carbene (NHC)-modified ligands to coordinate and stabilize luminescent CdSe-ZnS core-shell quantum dot (QD) dispersions in hydrophilic media. In particular, we probed the effects of ligand structure and coordination number on the coating affinity to the nanocrystals. We find that such NHC-based ligands rapidly coordinate onto the QDs (requiring ∼5-10 min of reaction time), which reflects the soft Lewis base nature of the NHC groups, with its two electrons sharing capacity. Removal of the hydrophobic cap and promotion of carbene-driven coordination on the nanocrystals have been verified by 1H NMR spectroscopy, while 13C NMR was used to identify the formation of carbene-Zn complexes. The newly coated QD dispersions exhibit great long-term colloidal stability over a wide range of conditions. Additionally, we find that coordination onto the QD surfaces affects the optical and spectroscopic properties of the nanocrystals. These include a size-dependent red-shift of the absorption and fluorescence spectra and a pronounced increase in the measured fluorescence intensity when the samples are stored under white light exposure compared to those stored in the dark.

Ligand-Mediated Release of Halides for Color Tuning of Perovskite Nanocrystals with Enhanced Stability.

The rich chemistry of metal halide perovskites has enabled various methods of band structure control and surface passivation. Here we report a highly facile and efficient post-treatment approach for precise color tuning of cesium lead halide perovskite nanocrystals (NCs) with enhanced stability. By utilizing a special multifunctional organic ligand, triphenyl(9-phenyl-9H-carbazol-3-yl)phosphonium bromide (TPP-Carz), carbon-halide bond cleavage can be achieved to release halide ions from halogenated solvents in a controlled manner for color tuning of perovskite NCs via ion exchange. Besides controlled release of halide ions for anion exchange, TPP-Carz can effectively passivate the surfaces of perovskite NCs simultaneously. As a result, perovskite NCs prepared by this post-treatment method with tunable colors over the entire visible spectrum have shown significantly improved luminescence and stability in comparison to the ones prepared using reactive anion precursors without surface passivation by TPP-Carz.

High-Temperature Grafting Silylation for Minimizing Leaching of Acid Functionality from Hydrophobic Mesoporous Silicas Used as Catalysts in the Liquid Phase.

Ordered-hexagonal silica materials, such as Mobil crystalline material-41 and Santa Barbara amorphous-15, have important applications in heterogeneous catalysis and biomass conversion due to their chemical stability and mesoporous structure. Low-temperature grafting (LG) is one of the most common functionalization methods used to modify the acidity/basicity or hydrophobicity/hydrophilicity of the surface. However, the materials prepared by this method are prone to leaching of functional groups into the reaction medium. The exact nature of the leaching phenomenon has not been fully addressed in the literature. In this contribution, we have investigated this process at the molecular level by combining well-controlled reaction experiments and several characterization techniques (Fourier transform infrared, 1H-29Si cross-polarization magic-angle spinning NMR, X-ray diffraction, thermogravimetric analysis, and N2 adsorption-desorption). We have found that leaching is originated by the presence of terminal surface silanols, which render the catalysts susceptible to the attack of water and polar compounds. Hence, instead of simple detaching of functional groups, leaching can be better described as a partial dissolution of the surface layers of the silica, which of course also removes the functional groups during this process. Therefore, an effective strategy to minimize leaching is to reduce the density of free silanols via full functionalization of the surface. We propose a novel silylation method, high-temperature grafting, which allows the grafting process to be conducted at high temperatures (180 °C) under solvent-free conditions. By this method, a more complete silylation of surface silanols can be obtained. Consequently, the samples prepared by this high-temperature grafting method show to be highly stable during acid-catalyzed alkylation reaction, conducted under severe conditions (high temperature and in the presence of polar solvents).

Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency.

Single crystalline zero-dimensional (0D) organic-inorganic hybrid materials with perfect host-guest structures have been developed as a new generation of highly efficient light emitters. Here we report a series of lead-free organic metal halide hybrids with a 0D structure, (C4N2H14X)4SnX6 (X = Br, I) and (C9NH20)2SbX5 (X = Cl), in which the individual metal halide octahedra (SnX64-) and quadrangular pyramids (SbX52-) are completely isolated from each other and surrounded by the organic ligands C4N2H14X+ and C9NH20+, respectively. The isolation of the photoactive metal halide species by the wide band gap organic ligands leads to no interaction or electronic band formation between the metal halide species, allowing the bulk materials to exhibit the intrinsic properties of the individual metal halide species. These 0D organic metal halide hybrids can also be considered as perfect host-guest systems, with the metal halide species periodically doped in the wide band gap matrix. Highly luminescent, strongly Stokes shifted broadband emissions with photoluminescence quantum efficiencies (PLQEs) of close to unity were realized, as a result of excited state structural reorganization of the individual metal halide species. Our discovery of highly luminescent single crystalline 0D organic-inorganic hybrid materials as perfect host-guest systems opens up a new paradigm in functional materials design.

Highly Efficient Broadband Yellow Phosphor Based on Zero-Dimensional Tin Mixed-Halide Perovskite.

Organic-inorganic hybrid metal halide perovskites have emerged as a highly promising class of light emitters, which can be used as phosphors for optically pumped white light-emitting diodes (WLEDs). By controlling the structural dimensionality, metal halide perovskites can exhibit tunable narrow and broadband emissions from the free-exciton and self-trapped excited states, respectively. Here, we report a highly efficient broadband yellow light emitter based on zero-dimensional tin mixed-halide perovskite (C4N2H14Br)4SnBrxI6-x (x = 3). This rare-earth-free ionically bonded crystalline material possesses a perfect host-dopant structure, in which the light-emitting metal halide species (SnBrxI6-x4-, x = 3) are completely isolated from each other and embedded in the wide band gap organic matrix composed of C4N2H14Br-. The strongly Stokes-shifted broadband yellow emission that peaked at 582 nm from this phosphor, which is a result of excited state structural reorganization, has an extremely large full width at half-maximum of 126 nm and a high photoluminescence quantum efficiency of ∼85% at room temperature. UV-pumped WLEDs fabricated using this yellow emitter together with a commercial europium-doped barium magnesium aluminate blue phosphor (BaMgAl10O17:Eu2+) can exhibit high color rendering indexes of up to 85.

Facile Conversion of Red Phosphorus into Soluble Polyphosphide Anions by Reaction with Potassium Ethoxide.

Soluble polyphosphide anions were successfully generated in a number of organic solvents by the reaction between shelf-stable red phosphorus and potassium ethoxide. The species were identified by (31)P NMR spectroscopy in solution and by X-ray crystal-structure determination of (Bu4N)2P16 in the solid state. The reaction was scaled up to gram quantities by using a flow-chemistry process.

Factors that Determine Zeolite Stability in Hot Liquid Water.

The susceptibility of zeolites to hot liquid water may hamper their full utilization in aqueous phase processes, such as those involved in biomass conversion and upgrading reactions. Interactions of zeolites with water strongly depend on the presence of hydrophilic moieties including Brønsted acid sites (BAS), extraframework cations, and silanol defects, which facilitate wetting of the surface. However, it is not clear which of these moieties are responsible for the susceptibility of zeolites to liquid water. Previous studies have offered contradictory explanations because the role of each of these characteristics has not been investigated independently. In this work, a systematic comparison has been attempted by relating crystallinity losses to the variation of each of the five zeolite characteristics that may influence their stability in liquid water, including number of BAS, Si-O-Si bonds, framework type, silanol defects, and extraframework Al. In this study, we have systematically monitored the crystallinity changes of a series of HY, H-ZSM-5, and H-ß zeolite samples with varying Si/Al ratio, density of BAS, zeolite structure, and density of silanol defects upon exposure to liquid water at 200 °C. The results of this comparison unambiguously indicate that the density of silanol defects plays the most crucial role in determining susceptibility of zeolites to hot liquid water. By functionalizing the silanol defects with organosilanes, the hydrophobicity of defective zeolite is increased and the tolerance to hot liquid water is significantly enhanced.

A tale of two metals: new cerium iron borocarbide intermetallics grown from rare-earth/transition metal eutectic fluxes.

R(33)Fe(14-x)Al(x+y)B(25-y)C(34) (R = La or Ce; x ≤ 0.9; y ≤ 0.2) and R(33)Fe(13-x)Al(x)B(18)C(34) (R = Ce or Pr; x < 0.1) were synthesized from reactions of iron with boron, carbon, and aluminum in R-T eutectic fluxes (T = Fe, Co, or Ni). These phases crystallize in the cubic space group Im3m (a = 14.617(1) Å, Z = 2, R(1) = 0.0155 for Ce(33)Fe(13.1)Al(1.1)B(24.8)C(34), and a = 14.246(8) Å, Z = 2, R(1) = 0.0142 for Ce(33)Fe(13)B(18)C(34)). Their structures can be described as body-centered cubic arrays of large Fe(13) or Fe(14) clusters which are capped by borocarbide chains and surrounded by rare earth cations. The magnetic behavior of the cerium-containing analogs is complicated by the possibility of two valence states for cerium and possible presence of magnetic moments on the iron sites. Temperature-dependent magnetic susceptibility measurements and Mössbauer data show that the boron-centered Fe(14) clusters in Ce(33)Fe(14-x)Al(x+y)B(25-y)C(34) are not magnetic. X-ray photoelectron spectroscopy data indicate that the cerium is trivalent at room temperature, but the temperature dependence of the resistivity and the magnetic susceptibility data suggest Ce(3+/4+) valence fluctuation beginning at 120 K. Bond length analysis and XPS studies of Ce(33)Fe(13)B(18)C(34) indicate the cerium in this phase is tetravalent, and the observed magnetic ordering at T(C) = 180 K is due to magnetic moments on the Fe(13) clusters.

Synthesis and properties of new multinary silicides R5Mg5Fe4Al(x)Si(18-x) (R = Gd, Dy, Y, x ≈ 12) grown in Mg/Al flux.

Reactions of iron, silicon, and R = Gd, Dy, or Y in 1:1 Mg/Al mixed flux produce well-formed crystals of R(5)Mg(5)Fe(4)Al(x)Si(18-x) (x ≈ 12). These phases have a new structure type in tetragonal space group P4/mmm (a = 11.655(2) Å, c = 4.0668(8) Å, Z = 1 and R(1) = 0.0155 for the Dy analogue). The structure features two rare earth sites and one iron site; the latter is in monocapped trigonal prismatic coordination surrounded by silicon and aluminum atoms. Siting of Al and Si was investigated using bond length analysis and (27)Al and (29)Si MAS NMR studies. The magnetic properties are determined by the R elements, with the Gd and Dy analogues exhibiting antiferromagnetic ordering at T(N) = 11.9 and 6.9 K respectively; both phases exhibit complex metamagnetic behavior with varying field.

Solid-state 17O NMR study of benzoic acid adsorption on metal oxide surfaces.

Solid-state (17)O NMR spectra of (17)O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the (17)O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. (27)Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

A 43Ca and 13C NMR study of the chemical interaction between poly(ethylene-vinyl acetate) and white cement during hydration.

(43)Ca and (13)C NMR methods were used to study the chemical interaction of poly(ethylene-vinyl acetate) (PEVAc) admixture in commercial-grade white cement. From (43)Ca NMR it is shown both that PEVAc induces modest changes in the hydrated cement structure, and that hydrated commercial cement is significantly more complex than models that have been used for its structure in past work. The (13)C NMR results show that the PEVAc hydrolysis occurs early in the cement hydration acceleration period, with a rate well-fit by an exponential decay using a time constant of 6±1 days.

Comprehensive chemical characterization of complexes involving lead-amino acid interactions.

Complexes of lead with L-phenylalanine, L-isoleucine, L-valine, or L-arginine have been isolated from reaction mixtures containing lead nitrate and the respective amino acid in acidic aqueous solution. The compounds have been comprehensively characterized using X-ray crystallography, solid state NMR spectroscopy and solution state NMR spectroscopy, IR and Raman spectroscopies, and electrospray ionization mass-spectrometry. The solid state structures of lead-phenylalanine, lead-valine, and lead-valine-isoleucine complexes show a lead center coordinated by two amino acid ligands, while the lead-arginine complex is a cluster involving two lead centers and three arginine molecules. The structural, spectroscopic, and spectrometric characterization of the complexes provides a basis to establish a fundamental understanding of heavy metal-amino acid interactions.

Surface alumina species on modified titanium dioxide: A solid-state (27)Al MAS and 3QMAS NMR investigation of catalyst supports.

(27)Al MAS and 3QMAS NMR have been used to study Al(2)O(3)/TiO(2) catalyst supports synthesized via excess-solution impregnation and surface sol-gel methods. Temperature and alumina loading level strongly affect chemical states of aluminum oxide species observed. Surface cations, Al(H2O)6(3+), a surface alumina monolayer, and disordered transitional aluminas (multilayers) and alpha-alumina, coexist on the TiO(2) surface. Chemical shift and quadrupole coupling constants are reported for the major species identified in 3QMAS experiments. Gold particle catalysts prepared from supports calcined at 500 degrees C have optimum catalytic activity in CO oxidation, and smallest gold particle size for supports, which show maximum monolayer type octahedral alumina on the titania surface.

A solid-state NMR study of the formation of molecular sieve SAPO-34.

This work examined the formation of a catalytically important microporous material, SAPO-34, in the presence of HF under hydrothermal synthesis conditions. The local environments of P, Al, F and Si atoms in several solid phases obtained at different stages of crystallization were characterized by several solid-state NMR techniques including (31)P, (27)Al, (19)F and (29)Si MAS, (27)Al triple-quantum MAS, (31)P{(27)Al} transfer of populations in double-resonance, (27)Al{(31)P} rotational-echo double-resonance (REDOR), (27)Al-->(31)P heteronuclear correlation spectroscopy, (31)P{(19)F} and (27)Al{(19)F} REDOR as well as (1)H-->(31)P cross polarization. The NMR results provide the new insights into the formation of SAPO-34.

17O solid-state NMR spectroscopic studies of the involvement of water vapor in molecular sieve formation by dry-gel conversion.

Dry-gel conversion is a relatively new approach for molecular sieve synthesis. This method potentially has several advantages over the traditional hydrothermal synthesis and can be used to prepare molecular sieves with certain unique properties. The technique involves treating the predried reactive gel powder with water vapor at elevated temperature and pressure. The role of water vapor in this apparent solid transformation is, however, not clear. In this work, we directly monitored the involvement of 17O-enriched water vapor in crystallization of AlPO4-11 (an aluminophosphate-based molecular sieve) by 17O solid-state NMR spectroscopy. In addition to 17O magic-angle spinning technique, several dipolar-coupling based double-resonance methods including 17O[27Al], 17O[31P] rotational-echo double-resonance, 17O --> 31P and 1H --> 17O cross polarization techniques were used for spectral editing to select different 17O species. The results show that water from the vapor phase slowly exchanges with water molecules strongly bound to the AlPO intermediates first. Then 17O atoms are gradually incorporated in both P-O-H and P-O-Al units in the layered intermediate. There are three different P sites in AlPO4-11. Interestingly, during the transformation from the layered intermediate to AlPO4-11, the 17O atoms prefer to bond to the P2 and P3, but not to P1. The absence of 17O atoms in the first coordination sphere of P1 site suggests that some building units such as joint four- and six-membered rings involving hydrogen bonding with structure-directing agents are common in both layered intermediate and AlPO4-11 and they are not affected by the transformation from the layered phase to the AlPO4-11 framework.