Photoelectrochemical Proton-Coupled Electron Transfer of TiO2 Thin Films on Silicon.

TiO2 thin films are often used as protective layers on semiconductors for applications in photovoltaics, molecule-semiconductor hybrid photoelectrodes, and more. Experiments reported here show that TiO2 thin films on silicon are electrochemically and photoelectrochemically reduced in buffered acetonitrile at potentials relevant to photoelectrocatalysis of CO2 reduction, N2 reduction, and H2 evolution. On both n-type Si and irradiated p-type Si, TiO2 reduction is proton-coupled with a 1e-:1H+ stoichiometry, as demonstrated by the Nernstian dependence of the Ti4+/3+ E1/2 on the buffer pKa. Experiments were conducted with and without illumination, and a photovoltage of ∼0.6 V was observed across 20 orders of magnitude in proton activity. The 4 nm films are almost stoichiometrically reduced under mild conditions. The reduced films catalytically transfer protons and electrons to hydrogen atom acceptors, based on cyclic voltammogram, bulk electrolysis, and other mechanistic evidence. TiO2/Si thus has the potential to photoelectrochemically generate high-energy H atom carriers. Characterization of the TiO2 films after reduction reveals restructuring with the formation of islands, rendering TiO2 films as a potentially poor choice as protecting films or catalyst supports under reducing and protic conditions. Overall, this work demonstrates that atomic layer deposition TiO2 films on silicon photoelectrodes undergo both chemical and morphological changes upon application of potentials only modestly negative of RHE in these media. While the results should serve as a cautionary tale for researchers aiming to immobilize molecular monolayers on "protective" metal oxides, the robust proton-coupled electron transfer reactivity of the films introduces opportunities for the photoelectrochemical generation of reactive charge-carrying mediators.

Free Energies of Proton-Coupled Electron Transfer Reagents and Their Applications.

We present an update and revision to our 2010 review on the topic of proton-coupled electron transfer (PCET) reagent thermochemistry. Over the past decade, the data and thermochemical formalisms presented in that review have been of value to multiple fields. Concurrently, there have been advances in the thermochemical cycles and experimental methods used to measure these values. This Review (i) summarizes those advancements, (ii) corrects systematic errors in our prior review that shifted many of the absolute values in the tabulated data, (iii) provides updated tables of thermochemical values, and (iv) discusses new conclusions and opportunities from the assembled data and associated techniques. We advocate for updated thermochemical cycles that provide greater clarity and reduce experimental barriers to the calculation and measurement of Gibbs free energies for the conversion of X to XHn in PCET reactions. In particular, we demonstrate the utility and generality of reporting potentials of hydrogenation, E°(V vs H2), in almost any solvent and how these values are connected to more widely reported bond dissociation free energies (BDFEs). The tabulated data demonstrate that E°(V vs H2) and BDFEs are generally insensitive to the nature of the solvent and, in some cases, even to the phase (gas versus solution). This Review also presents introductions to several emerging fields in PCET thermochemistry to give readers windows into the diversity of research being performed. Some of the next frontiers in this rapidly growing field are coordination-induced bond weakening, PCET in novel solvent environments, and reactions at material interfaces.

Unexpected "Spontaneous" Evolution of Catalytic, MOF-Supported Single Cu(II) Cations to Catalytic, MOF-Supported Cu(0) Nanoparticles.

A desirable feature of metal-organic frameworks (MOFs) is their well-defined structural periodicity and the presence of well-defined catalyst grafting sites (e.g., reactive -OH and -OH2 groups) that can support single-site heterogeneous catalysts. However, one should not overlook the potential role of residual organic moieties, specifically formate ions that can occupy the catalyst anchoring sites during MOF synthesis. Here we show how these residual formate species in a Zr-based MOF, NU-1000, critically alter the structure, redox capability, and catalytic activity of postsynthetically incorporated Cu(II) ions. Single-crystal X-ray diffraction measurements established that there are two structurally distinct types of Cu(II) ions in NU-1000: one type with residual formate and one without. In NU-1000 with formate, Cu(II) solely binds to the node via the formate-unoccupied, bridging µ3-OH, whereas in the formate-free case, it displaces protons from two node hydroxo ligands and resides close to the terminal -OH2. Under an inert atmosphere, node-bound formate facilitates the unanticipated reduction of isolated Cu(II) to nanoparticulate Cu(0)-a behavior which is essentially absent in the formate-free analogue because no other sacrificial reductant is present. When the two MOFs were tested as benzyl alcohol oxidation catalysts, we observed that residual formate boosts the catalytic turnover frequency. Density functional calculations showed that node-bound formate acts as a sacrificial two-electron donor and assists in reducing Cu(II) to Cu(0) by a nonradical pathway. The negative Gibbs free energy of reaction (ΔG) and enthalpy of reaction (ΔH) indicate that the reduction is thermodynamically favorable. The work presented here highlights how the often-neglected residual formate prevalent in nearly all zirconium-based MOFs can significantly modulate the properties of supported catalysts.

Interrogating Kinetic versus Thermodynamic Topologies of Metal-Organic Frameworks via Combined Transmission Electron Microscopy and X-ray Diffraction Analysis.

Synthetic protocols that preferentially result in metal-organic framework (MOF) crystallization of one topology over another remain an elusive, empirical process. This is primarily because of a lack of fundamental insights into MOF crystal growth and the effect of various experimental parameters on the resulting topologies. In this Communication, we demonstrate the temperature-topology relationship of MOFs constructed from hexanuclear oxozirconium cluster nodes and tetrakis(4-carboxylphenyl)porphyrin linkers via a combined transmission electron microscopy and powder X-ray diffraction study. Synthesis at room temperature led to a mixed phase consisting of 12-connected (assuming no defects) MOF-525 and 6-connected PCN-224, possessing ftw and she topologies, respectively. When the temperature was raised to 145 °C, 8-connected PCN-222 (csq topology) was found, with a possible concurrence of another 8-connected NU-902 (scu topology) and 12-connected PCN-223 (shp topology), in addition to MOF-525 and PCN-224. With an increase in reaction time at 145 °C, a change in product distribution was observed where PCN-222 remained the major crystal phase after 7 days, while the contribution from MOF-525 and PCN-224 decreased. These data suggest that MOF-525 and PCN-224 are the kinetic products while PCN-222 is the thermodynamic product.

Core-Shell Gold Nanorod@Zirconium-Based Metal-Organic Framework Composites as in Situ Size-Selective Raman Probes.

Nanoparticle encapsulation inside zirconium-based metal-organic frameworks (NP@MOF) is hard to control, and the resulting materials often have nonuniform morphologies with NPs on the external surface of MOFs and NP aggregates inside the MOFs. In this work, we report the controlled encapsulation of gold nanorods (AuNRs) by a scu-topology Zr-MOF, via a room-temperature MOF assembly. This is achieved by functionalizing the AuNRs with poly(ethylene glycol) surface ligands, allowing them to retain colloidal stability in the precursor solution and to seed the MOF growth. Using this approach, we achieve core-shell yields exceeding 99%, tuning the MOF particle size via the solution concentration of AuNRs. The functionality of AuNR@MOFs is demonstrated by using the AuNRs as embedded probes for selective surface-enhanced Raman spectroscopy (SERS). The AuNR@MOFs are able to both take-up or block molecules from the pores, thereby facilitating highly selective sensing at the AuNR ends. This proof-of-principle study serves to present both the outstanding level of control in the synthesis and the high potential for AuNR@Zr-MOF composites for SERS.

Stabilization of Formate Dehydrogenase in a Metal-Organic Framework for Bioelectrocatalytic Reduction of CO2.

The efficient fixation of excess CO2 from the atmosphere to yield value-added chemicals remains crucial in response to the increasing levels of carbon emission. Coupling enzymatic reactions with electrochemical regeneration of cofactors is a promising technique for fixing CO2 , while producing biomass which can be further transformed into biofuels. Herein, a bioelectrocatalytic system was established by depositing crystallites of a mesoporous metal-organic framework (MOF), termed NU-1006, containing formate dehydrogenase, on a fluorine-doped tin oxide glass electrode modified with Cp*Rh(2,2'-bipyridyl-5,5'-dicarboxylic acid)Cl2 complex. This system converts CO2 into formic acid at a rate of 79±3.4 mm h-1 with electrochemical regeneration of the nicotinamide adenine dinucleotide cofactor. The MOF-enzyme composite exhibited significantly higher catalyst stability when subjected to non-native conditions compared to the free enzyme, doubling the formic acid yield.

Beyond the Active Site: Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization.

To modify its steric and electronic properties as a support for heterogeneous catalysts, electron-withdrawing and electron-donating ligands, hexafluoroacetylacetonate (Facac-) and acetylacetonate (Acac-), were introduced to the metal-organic framework (MOF), NU-1000, via a process akin to atomic layer deposition (ALD). In the absence of Facac- or Acac-, NU-1000-supported, AIM-installed Ni(II) sites yield a mixture of C4, C6, C8, and polymeric products in ethylene oligomerization. (AIM = ALD-like deposition in MOFs). In contrast, both Ni-Facac-AIM-NU-1000 and Ni-Acac-AIM-NU-1000 exhibit quantitative catalytic selectivity for C4 species. Experimental findings are supported by density functional theory calculations, which show increases in the activation barrier for the C-C coupling step, due mainly to rearrangement of the siting of Facac- or Acac- to partially ligate added nickel. The results illustrate the important role of structure-tuning support modifiers in controlling the activity of MOF-sited heterogeneous catalysts and in engendering catalytic selectivity. The results also illustrate the ease with which crystallographically well-defined modifications of the catalyst support can be introduced when the node-coordinating molecular modifier is delivered via the vapor phase.

Fine-Tuning the Activity of Metal-Organic Framework-Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane.

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal-organic framework (MOF) NU-1000, have been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (<230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 followed by Co(II) ion deposition, yielding a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Using difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples, the promoter ions are sited between pairs of Zr6 nodes along the MOF c-axis, whereas the location of the cobalt ions varies with the promoter ions. These NU-1000-supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando X-ray absorption spectroscopy at the Co K-edge. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the following order: Mo(VI) < Ti(IV) < Al(III) < Zn(II) < Ni(II). The finding is attributed to increasing ease of formation of Co(III)-O• species and stabilization of a cobalt(III)-oxyl/propane transition state as the Lewis acidity of the promoter ions decreases. The results point to an increasing ability to fine-tune the structure-dependent activity of MOF-supported heterogeneous catalysts. Coupled with mechanistic studies-computational or experimental-this ability may translate into informed prediction of improved catalysts for propane ODH and other chemical reactions.

An Exceptionally Stable Metal-Organic Framework Supported Molybdenum(VI) Oxide Catalyst for Cyclohexene Epoxidation.

Molybdenum(VI) oxide was deposited on the Zr6 node of the mesoporous metal-organic framework NU-1000 via condensed-phase deposition where the MOF is simply submerged in the precursor solution, a process named solvothermal deposition in MOFs (SIM). Exposure to oxygen leads to a monodisperse, porous heterogeneous catalyst, named Mo-SIM, and its structure on the node was elucidated both computationally and spectroscopically. The catalytic activity of Mo-SIM was tested for the epoxidation of cyclohexene. Near-quantitative yields of cyclohexene oxide and the ring-opened 1,2-cyclohexanediol were observed, indicating activity significantly higher than that of molybdenum(VI) oxide powder and comparable to that of a zirconia-supported analogue (Mo-ZrO2) prepared in a similar fashion. Despite the well-known leaching problem of supported molybdenum catalysts (i.e., loss of Mo species thus causes deactivation), Mo-SIM demonstrated no loss in the metal loading before and after catalysis, and no molybdenum was detected in the reaction mixture. In contrast, Mo-ZrO2 led to significant leaching and close to 80 wt % loss of the active species. The stability of Mo-SIM was further confirmed computationally, with density functional theory calculations indicating that the dissociation of the molybdenum(VI) species from the node of NU-1000 is endergonic, corroborating the experimental data for the Mo-SIM material.

Lithium-coupled electron transfer reactions of nano-confined WOx within Zr-based metal-organic framework.

Interfacial charge transfer reactions involving cations and electrons are fundamental to (photo/electro) catalysis, energy storage, and beyond. Lithium-coupled electron transfer (LCET) at the electrode-electrolyte interfaces of lithium-ion batteries (LIBs) is a preeminent example to highlight the importance of charge transfer in modern-day society. The thermodynamics of LCET reactions define the minimal energy for charge/discharge of LIBs, and yet, these parameters are rarely available in the literature. Here, we demonstrate the successful incorporation of tungsten oxides (WOx) within a chemically stable Zr-based metal-organic framework (MOF), MOF-808. Cyclic voltammograms (CVs) of the composite, WOx@MOF-808, in Li+-containing acetonitrile (MeCN)-based electrolytes showed an irreversible, cathodic Faradaic feature that shifted in a Nernstian fashion with respect to the Li+ concentration, i.e., ∼59 mV/log [(Li+)]. The Nernstian dependence established 1:1 stoichiometry of Li+ and e-. Using the standard redox potential of Li+/0, the apparent free energy of lithiation of WOx@MOF-808 (ΔGapp,Li) was calculated to be -36 ± 1 kcal mol-1. ΔGapp,Li is an intrinsic parameter of WOx@MOF-808, and thus by deriving the similar reaction free energies of other metal oxides, their direct comparisons can be achieved. Implications of the reported measurements will be further contrasted to proton-coupled electron transfer (PCET) reactions on metal oxides.

Dissipation and Residue Pattern of Dinotefuran, Fluazinam, Indoxacarb, and Thiacloprid in Fresh and Processed Persimmon Using LC-MS/MS.

Pesticides which are diluted and sprayed according to the pre-harvest interval (PHI) are generally decomposed and lost through various factors and pathways, and the leftover pesticides are known as residual pesticides. This study aims to determine the dissipation of residual amounts of dinotefuran, fluazinam, indoxacarb, and thiacloprid in persimmon and the changes in the concentration of various processing products. Pesticide spraying is performed in accordance with the GAP (good agricultue practice) of Korea, and the processed products are manufactured using a conventional method after removing the skin of persimmons. The modified QuEchERS (Quick, Easy, Cheap, Effective, Rugged, and Safe) method and an optimized method using LC-MS/MS (liquid chromatography mass spectrometry) is implemented to analyze the residual pesticides. The linearity, recovery, and LOQ (limit of quantitation) are presented to verify the analysis method. The amount of residual pesticides tested decreases significantly in a time-dependent manner, regardless of the minimal dilution effect present due to growth. The residual concentration does not vary significantly during the processing stage despite the removal of the systemic pesticides, dinotefuran and thiacloprid. The residues of non-systemic pesticides, fluazinam and indoxacarb, are typically removed by the peeling removal and processing methods. The reduction factor of dinotefuran, whose residual concentration is increased, is less than 1, and the absolute amount of pesticides is decreased through processing. The results of this study can be used as the scientific basis data to ensure the safety of residual pesticides in processed products in the future.

Engineering Dendrimer-Templated, Metal-Organic Framework-Confined Zero-Valent, Transition-Metal Catalysts.

We describe and experimentally illustrate a strategy for synthesizing reactant-accessible, supported arrays of well-confined, sub-nanometer to 2 nm, metal(0) clusters and particles-here, copper, palladium, and platinum. The synthesis entails (a) solution-phase binding of metal ions by a generation-2 poly(amidoamine) (PAMAM) dendrimer, (b) electrostatic uptake of metalated, solution-dissolved, and positively charged dendrimers by the negatively charged pores of a zirconium-based metal-organic framework (MOF), NU-1000, and (c) chemical reduction of the incorporated metal ions. The pH of the unbuffered solution is known to control the overall charges of both the dendrimer guests and the hierarchically porous MOF. The combined results of electron microscopy, X-ray spectroscopy, and other measurements indicate the formation and microscopically uniform spatial distributions of zero-valent, monometallic Cu, Pd, and Pt species, with sizes depending strongly on the conditions and methods used for reduction of incorporated metal ions. Access to sub-nanometer clusters is ascribed to the stabilization effects imposed by the two templates (i.e., NU-1000 and dendrimer), which significantly limit the extent to which the metal atoms aggregate; as the thermal input increases, the dendrimer template gradually decomposes, allowing a further aggregation of metal clusters inside the hexagonal mesoporous channel of the MOF template, which ultimately self-limits at 3 nm (i.e., the mesopore width of NU-1000). Using CO oxidation and n-hexene hydrogenation as model reactions in the gas and condensed phases, we show that the dual-templated metal species can act as stable, efficient heterogeneous catalysts.

Realization of Lithium-Ion Capacitors with Enhanced Energy Density via the Use of Gadolinium Hexacyanocobaltate as a Cathode Material.

Li-ion storage devices having superior energy density are critical for one-time-charge long-term applications. Currently, much research endeavor is directed at enhancing the energy density of hybrid Li-ion capacitors, which incorporate the high energy of conventional Li-ion batteries with the elevated power density of Li-ion supercapacitors. Herein, we prepare orthorhombic GdCo(CN)6 as a new Prussian blue analogue (PBA), showing that this compound offers excellent energy/power densities (605 W·h kg-1 and 174 W kg-1, respectively) and features Li-ion storage capacities (352 and 258 mA·h gelectrode-1 at 100 and 1000 mA g-1, respectively) that are almost twice higher than those of other cathode materials utilized in hybrid Li-ion capacitors. Thus, this study not only opens a new path for the exploration of new-type PBAs, but also provides insights on the use of lanthanides in energy storage applications.

A Bismuth Metal-Organic Framework as a Contrast Agent for X-ray Computed Tomography.

A new bismuth metal-organic framework (MOF), bismuth-NU-901 (Bi-NU-901), featuring the scu topology and a pore with a diameter of ∼11 Å, was solvothermally synthesized, and its use as an X-ray computed tomography (CT) contrast agent was tested. X-ray CT is a common diagnostic method used in the medical field. Inside the body, contrast media enhance the distinction between tissues and organs of similar density. Bi-NU-901 consists of eight connected Bi6 nodes and tetratopic 1,3,5,8-(p-benzoate)pyrene linkers (TBAPy). Numerous material characterization studies including powder X-ray diffraction (PXRD), scanning transmission electron microscopy (STEM), and DFT pore size distribution support the scu structure. Additionally, given the framework's high density of nontoxic heavy atoms, Bi-NU-901 was evaluated as an X-ray computed tomography (CT) agent. Importantly, in vitro studies revealed this new bismuth MOF demonstrates ∼7 times better contrast intensity compared to a zirconium MOF featuring the same topology and ∼14 times better contrast than a commercially available CT contrast agent. These results suggest bismuth MOFs may be promising CT contrast agents.

Effect of Redox "Non-Innocent" Linker on the Catalytic Activity of Copper-Catecholate-Decorated Metal-Organic Frameworks.

Two new UiO-68 type of Zr-MOFs featuring redox non-innocent catechol-based linkers of different redox activities have been synthesized through a de novo mixed-linker strategy. Metalation of the MOFs with Cu(II) precursors triggers the reduction of Cu(II) by the phenyl-catechol groups to Cu(I) with the concomitant formation of semiquinone radicals as evidenced by EPR and XPS characterization. The MOF-supported catalysts are selective toward the allylic oxidation of cyclohexene and it is found that the presence of in situ-generated Cu(I) species exhibits enhanced catalytic activity as compared to a similar MOF with Cu(II) metalated naphthalenyl-dihydroxy groups. This work unveils the importance of metal-support redox interactions in the catalytic activity of MOF-supported catalysts which are not easily accessible in traditional metal oxide supports.

Superconducting junction of a single-crystalline au nanowire for an ideal Josephson device.

We report on the fabrication and measurements of a superconducting junction of a single-crystalline Au nanowire, connected to Al electrodes. The current-voltage characteristic curve shows a clear supercurrent branch below the superconducting transition temperature of Al and quantized voltage plateaus on application of microwave radiation, as expected from Josephson relations. Highly transparent (0.95) contacts very close to an ideal limit of 1 are formed at the interface between the normal metal (Au) and the superconductor (Al). The very high transparency is ascribed to the single crystallinity of a Au nanowire and the formation of an oxide-free contact between Au and Al. The subgap structures of the differential conductance are well explained by coherent multiple Andreev reflections (MAR), the hallmark of mesoscopic Josephson junctions. These observations demonstrate that single crystalline Au nanowires can be employed to develop novel quantum devices utilizing coherent electrical transport.