Predictive Removal of Interfacial Defect-Induced Trap States between Titanium Dioxide Nanoparticles via Sub-Monolayer Zirconium Coating.

First principles modeling of anatase TiO2 surfaces and their interfacial contacts shows that defect-induced trap states within the band gap arise from intrinsic structural distortions, and these can be corrected by modification with Zr(IV) ions. Experimental testing of these predictions has been undertaken using anatase nanocrystals modified with a range of Zr precursors and characterized using structural and spectroscopic methods. Continuous-wave electron paramagnetic resonance (EPR) spectroscopy revealed that under illumination, nanoparticle-nanoparticle interfacial hole trap states dominate, which are significantly reduced after optimizing the Zr doping. Fabrication of nanoporous films of these materials and charge injection using electrochemical methods shows that Zr doping also leads to improved electron conductivity and mobility in these nanocrystalline systems. The simple methodology described here to reduce the concentration of interfacial defects may have wider application to improving the efficiency of systems incorporating metal oxide powders and films including photocatalysts, photovoltaics, fuel cells, and related energy applications.

Solar-to-Chemical Fuel Conversion via Metal Halide Perovskite Solar-Driven Electrocatalysis.

Sunlight is an abundant and clean energy source, the harvesting of which could make a significant contribution to society's increasing energy demands. Metal halide perovskites (MHP) have recently received attention for solar fuel generation through photocatalysis and solar-driven electrocatalysis. However, MHP photocatalysis is limited by low solar energy conversion efficiency, poor stability, and impractical reaction conditions. Compared to photocatalysis, MHP solar-driven electrocatalysis not only exhibits higher solar conversion efficiency but also is more stable when operating under practical reaction conditions. In this Perspective, we outline three leading types of MHP solar-driven electrocatalysis device technologies now in the research spotlight, namely, (1) photovoltaic-electrochemical (PV-EC), (2) photovoltaic-photoelectrochemical (PV-PEC), and (3) photoelectrochemical (PEC) approaches for solar-to-fuel reactions, including water-splitting and the CO2 reduction reaction. In addition, we compare each technology to show their relative technical advantages and limitations and highlight promising research directions for the rapidly emerging scientific field of MHP-based solar-driven electrocatalysis.

Electrocatalytic Proton Reduction by a Cobalt(III) Hydride Complex with Phosphinopyridine PN Ligands.

Cobalt complexes with 2-(diisopropylphosphinomethyl)pyridine (PN) ligands have been synthesized with the aim of demonstrating electrocatalytic proton reduction to dihydrogen with a well-defined hydride complex of an Earth-abundant metal. Reactions of simple cobalt precursors with 2-(diisopropylphosphino-methyl)pyridine (PN) yield [CoII(PN)2(MeCN)][BF4]2 1, [CoIII(PN)2(H)(MeCN)][PF6]2 2, and [CoIII(PN)2(H)(Cl)][PF6] 3. Complexes 1 and 3 have been characterized crystallographically. Unusually for a bidentate PN ligand, all three exhibit geometries with mutually trans phosphorus and nitrogen ligands. Complex 1 exhibits a distorted square-pyramidal geometry with an axial MeCN ligand in a low-spin electronic state. In complexes 2 and 3, the PN ligands lie in a plane leaving the hydride trans to MeCN or chloride, respectively. The redox behavior of the three complexes has been studied by cyclic voltammetry at variable scan rates and by spectroelectrochemistry. A catalytic wave is observed in the presence of trifluoroacetic acid (TFA) at an applied potential close to the Co(II/I) couple of 1. Bulk electrolysis of 1, 2, or 3 at a potential of ca. -1.4 V vs E(Fc+/Fc) in the presence of TFA yields H2 with Faradaic yields close to 100%. A catalytic mechanism is proposed in which the pyridine moiety of a PN ligand acts as a pendant proton donor following opening of the chelate ring. Additional mechanisms may also operate, especially in the presence of high acid concentration where speciation changes.

Carbon Nitride as a Ligand: Selective Hydrogenation of Terminal Alkenes Using [(η5 -C5 Me5 )IrCl(g-C3 N4 -κ2 N,N')]Cl.

Anchoring a homogeneous catalyst onto a heterogeneous support facilitates separation of the product from the catalyst, and catalyst-substrate interactions can also modify reactivity. Herein we describe the synthesis of composite materials comprising carbon nitride (g-C3 N4 ) as the heterogeneous support and the well-established homogeneous catalyst moiety [Cp*IrCl]+ (where Cp*=η5 -C5 Me5 ), commonly used for catalytic hydrogenation. Coordination of [Cp*IrCl]+ to g-C3 N4 occurs directly at exposed edge sites with a κ2 N,N' binding motif, leading to a primary inner coordination sphere analogous to known homogeneous complexes of the general class [Cp*IrCl(NN-κ2 N,N')]+ (where N,N'=a bidentate nitrogen ligand). Hydrogenation of unsaturated substrates using the composite catalyst is selective for terminal alkenes, which is attributed to the restricted steric environment of the outer coordination sphere at the edge-sites of g-C3 N4 .

Carbon nitride as a ligand: edge-site coordination of ReCl(CO)3-fragments to g-C3N4.

IR spectroscopy and model structural studies show binding of ReCl(CO)3-fragments to carbon nitride (g-C3N4) occurs viaκ2 N,N' bidentate coordination.

Structure of Amido Pyridinium Betaines: Persistent Intermolecular C-H⋠⋠⋠N Hydrogen Bonding in Solution.

A hydrogen bond of the type C-H⋅⋅⋅X (X=O or N) is known to influence the structure and function of chemical and biological systems in solution. C-H⋅⋅⋅O hydrogen bonding in solution has been extensively studied, both experimentally and computationally, whereas the equivalent thermodynamic parameters have not been enumerated experimentally for C-H⋅⋅⋅N hydrogen bonds. This is, in part, due to the lack of systems that exhibit persistent C-H⋅⋅⋅N hydrogen bonds in solution. Herein, a class of molecule based on a biologically active norharman motif that exhibits unsupported intermolecular C-H⋅⋅⋅N hydrogen bonds in solution has been described. A pairwise interaction leads to dimerisation to give bond strengths of about 7 kJ mol-1 per hydrogen bond, which is similar to chemically and biologically relevant C-H⋅⋅⋅O hydrogen bonding. The experimental data is supported by computational work, which provides additional insight into the hydrogen bonding by consideration of electrostatic and orbital interactions and allowed a comparison between calculated and extrapolated NMR chemical shifts.

Enhancement of hydrogen production using photoactive nanoparticles on a photochemically inert photonic macroporous support.

The propagation of light in photonic materials can be modified to increase the probability of photon absorption. Here we report the synthesis of composite materials comprising a photochemically inert photonic macroporous ZrO2 support decorated with photocatalytically active CdS nanoparticles. The relative energies of valence and conduction bands restrict photon absorption and catalysis to the CdS nanoparticles. The generation of hydrogen from water under visible light illumination (>400 nm) has been studied as a function of the photonic support. A maximum 4.7 fold enhancement in hydrogen production is observed compared to a non-photonic support when the absorption band of the CdS nanoparticles partially overlaps with the blue edge of the photonic ZrO2 stop band. This general strategy supports the independent optimization of optical and photochemical processes to increase the overall conversion efficiency of solar to chemical energy.

Enhanced photocatalytic hydrogen generation using polymorphic macroporous TaON.

Macroporous TaON (mac-TaON) is prepared using polymer sphere templating and controlled ammonolysis. In contrast to typical powder synthesis, which gives the ß polymorph, mac-TaON is a mixture of ß and γ polymorphs. mac-TaON shows twice the activity for photocatalytic hydrogen generation in comparison to mac-TaON when normalised for surface area.

Charged behaviour from neutral ligands: synthesis and properties of N-heterocyclic pseudo-amides.

Deprotonation of the 1-isopropyl-3-(phenylamino)pyridin-1-ium iodide gives the corresponding neutral betaine, which is formalised as a pyridinium-amido ligand when coordinated to a metal. Spectroscopic, structural and theoretical methods have been used to investigate the metal-ligand bonding, ligand dynamics and electron distribution. Collectively, the data show that the ligand can be characterised as a pseudo-amide and is a strong donor akin to alkyl phosphines and N-heterocyclic carbenes. Furthermore, rotation about both N substituent C-N bonds occurs, which is in contrast to the two alternative pyridinium positional isomers that exhibit neutral resonance structures. For comparison, compounds and complexes derived from norharman were prepared, which contain an additional C-C bond supporting conjugation and the accessibility of a neutral resonance structure. Notwithstanding the formal neutral structure, norharman-derived ligands are comparably strong donors, and have the additional advantage of exhibiting stability to dioxygen and water.

Microwave plasma synthesis of lanthanide zirconates from microwave transparent oxides.

Lanthanide zirconate phases Ln(2)Zr(2)O(7) and Ln(4)Zr(3)O(12) (Ln = Y, La, Gd, Dy, Ho, Yb) have been prepared using a microwave induced plasma methodology, which allows rapid synthesis using materials which do not couple directly with microwaves at room temperature. We describe the measurement of heating profiles of the precursor binary metal oxides which can be used to identify conditions conducive to the synthesis of more complex oxides. Uncontrolled heating which can be a feature of microwave synthesis of ceramics is not observed, allowing reproducible synthesis. Conventionally these phases are prepared at >1400 °C over hours or days and are being investigated for applications including the immobilisation of nuclear waste where rapid processing is important. Using the microwave plasma method, phase-pure materials have been prepared in minutes. Furthermore, it is clear that Ln(2)Zr(2)O(7) and Ln(4)Zr(3)O(12) also exhibit significant plasma-promoted dielectric heating (e.g. >2200 °C for Dy(4)Zr(3)O(12)) which is typically greater than either of the respective precursors, thus providing a driving force to rapidly complete the reaction.

ß-Carboline (norharman).

The structure of ß-carboline, also called norharman (systematic name: 9H-pyrido[3,4-b]indole), C(11)H(8)N(2), has been determined at 110 K. Norharman is prevalent in the environment and the human body and is of wide biological interest. The structure exhibits intermolecular N-H···N hydrogen bonding, which results in a one-dimensional herringbone motif. The three rings of the norharman molecule collectively result in a C-shaped curvature of 3.19 (13)° parallel to the long axis. The diffraction data show shorter pyridyl C-C bonds than those reported at the STO-3G level of theory.

Microwave-induced plasma heating and synthesis: in situ temperature measurement of metal oxides and reactions to form ternary oxides.

Direct microwave synthesis between solids is limited by the restricted number of materials that exhibit microwave heating at room temperature. The dielectric properties of most materials dictate that microwave heating can occur at higher temperatures, primarily due to increasing conduction losses. Microwave-induced plasma promoted microwave heating circumvents the requirement for room temperature microwave heating allowing microwave methods to be applied to a greater range of materials. For example, MgO heats to >1700 degrees C using an O(2) plasma and 900 W magnetron power. Here we demonstrate that in situ temperature measurements can be used to identify binary oxides that exhibit significant plasma promoted heating. Furthermore, reactions to form ternary oxides can be monitored to determine if reactions are driven by the dielectric properties of the precursor(s) or product.

Synthesis, coordination chemistry and bonding of strong N-donor ligands incorporating the 1H-pyridin-(2E)-ylidene (PYE) motif.

A range of N-donor ligands based on the 1H-pyridin-(2E)-ylidene (PYE) motif have been prepared, including achiral and chiral examples. The ligands incorporate one to three PYE groups that coordinate to a metal through the exocyclic nitrogen atom of each PYE moiety, and the resulting metal complexes have been characterised by methods including single-crystal X-ray diffraction and NMR spectroscopy to examine metal-ligand bonding and ligand dynamics. Upon coordination of a PYE ligand to a proton or metal-complex fragment, the solid-state structures, NMR spectroscopy and DFT studies indicate that charge redistribution occurs within the PYE heterocyclic ring to give a contribution from a pyridinium-amido-type resonance structure. Additional IR spectroscopy and computational studies suggest that PYE ligands are strong donor ligands. NMR spectroscopy shows that for metal complexes there is restricted motion about the exocyclic C-N bond, which projects the heterocyclic N-substituent in the vicinity of the metal atom causing restricted motion in chelating-ligand derivatives. Solid-state structures and DFT calculations also show significant steric congestion and secondary metal-ligand interactions between the metal and ligand C-H bonds.

Addition of N-heterocyclic carbenes to imines: phenoxide assisted deprotonation of an imidazolium moiety and generation of breslow intermediates derived from imines.

Reactions between imidazolium-imine salts and base result in C-C bond formation via intermediate N-heterocyclic carbenes. In the presence of a proximal OH moiety, carbene formation occurs via intramolecular deprotonation by phenoxide. For simple imines, a reactive Breslow-type intermediate gives access to new heterocycles with the formation of six- and seven-member rings.

Synthesis of rhodium(I) and iridium(I) complexes of chiral N-heterocyclic carbenes and their application to asymmetric transfer hydrogenation.

Rhodium and iridium complexes of chiral NHC-phenolimine and NHC-amine ligands have been prepared and studied for asymmetric transfer hydrogenation. X-ray and NMR spectroscopy show that for NHC-phenolimine complexes abstraction of chloride results in a change in ligand coordination from NHC only to chelating NHC-imine. Complexes of NHC-amines are inactive for transfer hydrogenation, whereas complexes of NHC-phenolimines are active at room temperature for a range of aryl containing ketones. Enantioselectivity is very sensitive to the NHC N-substituent resulting in a switch in the predominant enantiomer.

Molybdenum and tungsten structural differences are dependent on ndz(2)/(n + 1)s mixing: comparisons of (silox)3MX/R (M = Mo, W; silox = (t)Bu3SiO).

Treatment of trans-(Et 2O) 2MoCl 4 with 2 or 3 equiv of Na(silox) (i.e., NaOSi (t) Bu 3) afforded (silox) 3MoCl 2 ( 1-Mo) or (silox) 3MoCl ( 2-Mo). Purification of 2-Mo was accomplished via addition of PMe 3 to precipitate (silox) 3ClMoPMe 3 ( 2-MoPMe 3), followed by thermolysis to remove phosphine. Use of MoCl 3(THF) 3 with various amounts of Na(silox) produced (silox) 2ClMoMoCl(silox) 2 ( 3-Mo). Alkylation of 2-Mo with MeMgBr or EtMgBr afforded (silox) 3MoR (R = Me, 2-MoMe; Et, 2-MoEt). 2-MoEt was also synthesized from C 2H 4 and (silox) 3MoH, which was prepared from 2-Mo and NaBEt 3H. Thermolysis of WCl 6 with HOSi ( t )Bu 3 afforded (silox) 2WCl 4 ( 4-W), and sequential treatment of 4-W with Na/Hg and Na(silox) provided (silox) 3WCl 2 ( 1-W, tbp, X-ray), which was alternatively prepared from trans-(Et 2S) 2WCl 4 and 3 equiv of Tl(silox). Na/Hg reduction of 1-W generated (silox) 3WCl ( 2-W). Alkylation of 2-W with MeMgBr produced (silox) 3WMe ( 2-WMe), which dehydrogenated to (silox) 3WCH ( 6-W) with Delta H (double dagger) = 14.9(9) kcal/mol and Delta S (double dagger) = -26(2) eu. Magnetism and structural studies revealed that 2-Mo and 2-MoEt have triplet ground states (GS) and distorted trigonal monopyramid (tmp) and tmp structures, respectively. In contrast, 2-W and 2-WMe possess squashed-T d (distorted square planar) structures, and the former has a singlet GS. Quantum mechanics/molecular mechanics studies of the S = 0 and S = 1 states for full models of 2-Mo, 2-MoEt, 2-W, and 2-WMe corroborate the experimental findings and are consistent with the greater nd z (2) /( n + 1)s mixing in the third-row transition-metal species being the dominant feature in determining the structural disparity between molybdenum and tungsten.

Structural variation, dynamics, and catalytic application of palladium(II) complexes of di-N-heterocyclic carbene-amine ligands.

A series of palladium(II) complexes incorporating di-NHC-amine ligands has been prepared and their structural, dynamic and catalytic behaviour investigated. The complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))PdCl(2)] (12) and [trans-(kappa(2)-(Mes)CN(H)C(Mes))PdCl(2)] (13) do not exhibit interaction between the amine nitrogen and palladium atom respectively. NMR spectroscopy between -40 and 25 degrees C shows that the di-NHC-amine ligand is flexible expressing C(s) symmetry and for 13 rotation of the mesityl groups is prevented. In the related C(1) complex [(kappa(3)-(tBu)CN(H)C(tBu))PdCl][Cl] (14) coordination of NHC moieties and amine nitrogen atom is observed between -40 and 25 degrees C. Reaction between 12-14 and two equivalents of AgBF(4) in acetonitrile gives the analogous complexes [trans-(kappa(2)-(tBu)CN(Bn)C(tBu))Pd(MeCN)(2)][BF(4)](2) (15), [trans-(kappa(2)-(Mes)CN(H)C(Mes))Pd(MeCN)(2)][BF(4)](2) (16) and [(kappa(3)-(tBu)CN(H)C(tBu))Pd(MeCN)][BF(4)](2) (17) indicating that ligand structure determines amine coordination. The single crystal X-ray structures of 12, 17 and two ligand imidazolium salt precursors (tBu)C(H)N(Bn)C(H)(tBu)][Cl](2) (2) and [(tBu)C(H)N(H)C(H)(tBu)][BPh(4)](2) (4) have been determined. Complexes 12-14 and 15-17 have been shown to be active precatalysts for Heck and hydroamination reactions respectively.

Microwave-induced plasma-promoted materials synthesis.

The discovery of new materials requires the development of a diversity of synthetic techniques. Microwave methods offer the opportunity to synthesise and modify the composition, structure and morphology of materials, particularly composites via differential heating. Microwave-induced plasmas (MIPs) allow any solid mixture to be heated, and can promote direct microwave heating at elevated temperature, greatly expanding the use of microwaves for reactions between solids and gas-solid mixtures.

Plasma-promoted dielectric heating in the microwave synthesis of spinels.

Comparison between the rates of synthesis of the spinel phases (MAl2O4, M = Mg, Zn, Ni; and MFe2O4, M = Mg, Zn, Mn) using an O2 microwave-induced plasma (MIP) and conventional (tube furnace) methods indicate that a MIP promotes microwave dielectric heating at elevated temperatures.

A new polymorph and two inclusion compounds of 9,9'-spirobifluorene.

Two new inclusion compounds of 9,9'-spirobifluorene (SBF) incorporating benzene [(I), C25H16.C6H6] and biphenyl [(II), C25H16.C12H10], and a new polymorph of SBF [(III), C25H16] are reported. All three exhibit C-H...pi(arene) hydrogen bonds between adjacent SBF molecules. Compound (II) also contains biphenyl C-H to SBF pi-arene interactions. Collectively, hydrogen bonding gives rise to a chain and a layered motif in compounds (I) and (II), respectively.