Magnetic Exchange Coupling in Zeolite Copper Dimers and Its Contribution to Methane Activation.

The highly reactive binuclear [Cu2O]2+ active site in copper zeolites activates the inert C-H bond of methane at low temperatures, offering a potential solution to reduce methane flaring and mitigate atmospheric methane levels. While substantial progress has been made in understanding the activation of methane by this core, one critical aspect, the active site's spin, has remained undetermined. In this study, we use variable-temperature, variable-field magnetic circular dichroism spectroscopy to define the ground state spin of the [Cu2O]2+ active sites in Cu-CHA and Cu-MFI. This novel approach allows for site-selective determination of the magnetic exchange coupling between the two copper centers of specific [Cu2O]2+ cores in a heterogeneous mixture, circumventing the drawbacks of bulk magnetic techniques. These experimental findings are coupled to density functional theory calculations to elucidate magnetostructural correlations in copper zeolites that are different from those of homogeneous binuclear Cu(II) complexes. The different spin states for the [Cu2O]2+ cores have different reactivities governed by how methane approaches the active site. This introduces a new understanding of zeolite topological control on active site reactivity.

In Situ UV-Vis-NIR Absorption Spectroscopy and Catalysis.

This review highlights in situ UV-vis-NIR range absorption spectroscopy in catalysis. A variety of experimental techniques identifying reaction mechanisms, kinetics, and structural properties are discussed. Stopped flow techniques, use of laser pulses, and use of experimental perturbations are demonstrated for in situ studies of enzymatic, homogeneous, heterogeneous, and photocatalysis. They access different time scales and are applicable to different reaction systems and catalyst types. In photocatalysis, femto- and nanosecond resolved measurements through transient absorption are discussed for tracking excited states. UV-vis-NIR absorption spectroscopies for structural characterization are demonstrated especially for Cu and Fe exchanged zeolites and metalloenzymes. This requires combining different spectroscopies. Combining magnetic circular dichroism and resonance Raman spectroscopy is especially powerful. A multitude of phenomena can be tracked on transition metal catalysts on various supports, including changes in oxidation state, adsorptions, reactions, support interactions, surface plasmon resonances, and band gaps. Measurements of oxidation states, oxygen vacancies, and band gaps are shown on heterogeneous catalysts, especially for electrocatalysis. UV-vis-NIR absorption is burdened by broad absorption bands. Advanced analysis techniques enable the tracking of coking reactions on acid zeolites despite convoluted spectra. The value of UV-vis-NIR absorption spectroscopy to catalyst characterization and mechanistic investigation is clear but could be expanded.

Stabilizing Au2+ in a mixed-valence 3D halide perovskite.

Although Cu2+ is ubiquitous, the relativistic destabilization of the 5d orbitals makes the isoelectronic Au2+ exceedingly rare, typically stabilized only through Au-Au bonding or by using redox non-innocent ligands. Here we report the perovskite Cs4AuIIAuIII2Cl12, an extended solid with mononuclear Au2+ sites, which is stable to ambient conditions and characterized by single-crystal X-ray diffraction. The 2+ oxidation state of Au was assigned using 197Au Mössbauer spectroscopy, electron paramagnetic resonance, and magnetic susceptibility measurements, with comparison to paramagnetic and diamagnetic analogues with Cu2+ and Pd2+, respectively, as well as to density functional theory calculations. This gold perovskite offers an opportunity to study the optical and electronic transport of the uncommon Au2+/3+ mixed-valence state and the characteristics of the elusive Au2+ ion coordinated to simple ligands. Compared with the perovskite Cs2AuIAuIIICl6, which has been studied since the 1920s, Cs4AuIIAuIII2Cl12 exhibits a 0.7 eV reduction in optical absorption onset and a 103-fold increase in electronic conductivity.

Tuning Copper Active Site Composition in Cu-MOR through Co-Cation Modification for Methane Activation.

The industrial implementation of a direct methane to methanol process would lead to environmental and economic benefits. Copper zeolites successfully execute this reaction at relatively low temperatures, and mordenite zeolites in particular enable high methanol production. When loaded to a Cu/Al ratio of 0.45, mordenite (Si/Al 5 to 9) has been shown to host three active sites: two [CuOCu]2+ sites labeled MOR1 and MOR2, and a mononuclear [CuOH]+ site. Also at low copper loadings (Cu/Al < 0.20), mordenite has been demonstrated to activate methane, but its active site has never been reported. Here, we investigate Na+ mordenite with varying copper loadings to better understand copper speciation in mordenite. At low copper loadings, we uncover an unidentified active site ('MOR3') with a strong overlap with the [CuOH]+ site's spectroscopic signal. By changing the co-cation, we selectively speciate more MOR3 relative to [CuOH]+, allowing its identification as a [CuOCu]2+ site. Active site identification in heterogeneous catalysts is a frequent problem due to signal overlap. By changing cation composition, we introduce an innovative method for simplifying a material to allow better analysis. This has implications for the study of Cu zeolites for methane to methanol and NOx catalysis, but also for studying and tuning heterogeneous catalysts in general.

Methane Activation by a Mononuclear Copper Active Site in the Zeolite Mordenite: Effect of Metal Nuclearity on Reactivity.

The direct conversion of methane to methanol would have a wide reaching environmental and industrial impact. Copper-containing zeolites can perform this reaction at low temperatures and pressures at a previously defined O2-activated [Cu2O]2+ site. However, after autoreduction of the copper-containing zeolite mordenite and removal of the [Cu2O]2+ active site, the zeolite is still methane reactive. In this study, we use diffuse reflectance UV-vis spectroscopy, magnetic circular dichroism, resonance Raman spectroscopy, electron paramagnetic resonance, and X-ray absorption spectroscopy to unambiguously define a mononuclear [CuOH]+ as the CH4 reactive active site of the autoreduced zeolite. The rigorous identification of a mononuclear active site allows a reactivity comparison to the previously defined [Cu2O]2+ active site. We perform kinetic experiments to compare the reactivity of the [CuOH]+ and [Cu2O]2+ sites and find that the binuclear site is significantly more reactive. From the analysis of density functional theory calculations, we elucidate that this increased reactivity is a direct result of stabilization of the [Cu2OH]2+ H-atom abstraction product by electron delocalization over the two Cu cations via the bridging ligand. This significant increase in reactivity from electron delocalization over a binuclear active site provides new insights for the design of highly reactive oxidative catalysts.

Second-Sphere Lattice Effects in Copper and Iron Zeolite Catalysis.

Transition-metal-exchanged zeolites perform remarkable chemical reactions from low-temperature methane to methanol oxidation to selective reduction of NOx pollutants. As with metalloenzymes, metallozeolites have impressive reactivities that are controlled in part by interactions outside the immediate coordination sphere. These second-sphere effects include activating a metal site through enforcing an "entatic" state, controlling binding and access to the metal site with pockets and channels, and directing radical rebound vs cage escape. This review explores these effects with emphasis placed on but not limited to the selective oxidation of methane to methanol with a focus on copper and iron active sites, although other transition-metal-ion zeolite reactions are also explored. While the actual active-site geometric and electronic structures are different in the copper and iron metallozeolites compared to the metalloenzymes, their second-sphere interactions with the lattice or the protein environments are found to have strong parallels that contribute to their high activity and selectivity.

Atmospheric methane removal: a research agenda.

Atmospheric methane removal (e.g. in situ methane oxidation to carbon dioxide) may be needed to offset continued methane release and limit the global warming contribution of this potent greenhouse gas. Because mitigating most anthropogenic emissions of methane is uncertain this century, and sudden methane releases from the Arctic or elsewhere cannot be excluded, technologies for methane removal or oxidation may be required. Carbon dioxide removal has an increasingly well-established research agenda and technological foundation. No similar framework exists for methane removal. We believe that a research agenda for negative methane emissions-'removal' or atmospheric methane oxidation-is needed. We outline some considerations for such an agenda here, including a proposed Methane Removal Model Intercomparison Project (MR-MIP). This article is part of a discussion meeting issue 'Rising methane: is warming feeding warming? (part 1)'.

Alloying a single and a double perovskite: a Cu+/2+ mixed-valence layered halide perovskite with strong optical absorption.

Introducing heterovalent cations at the octahedral sites of halide perovskites can substantially change their optoelectronic properties. Yet, in most cases, only small amounts of such metals can be incorporated as impurities into the three-dimensional lattice. Here, we exploit the greater structural flexibility of the two-dimensional (2D) perovskite framework to place three distinct stoichiometric cations in the octahedral sites. The new layered perovskites AI 4[CuII(CuIInIII)0.5Cl8] (1, A = organic cation) may be derived from a CuI-InIII double perovskite by replacing half of the octahedral metal sites with Cu2+. Electron paramagnetic resonance and X-ray absorption spectroscopy confirm the presence of Cu2+ in 1. Crystallographic studies demonstrate that 1 represents an averaging of the CuI-InIII double perovskite and CuII single perovskite structures. However, whereas the highly insulating CuI-InIII and CuII perovskites are colorless and yellow, respectively, 1 is black, with substantially higher electronic conductivity than that of either endmember. We trace these emergent properties in 1 to intervalence charge transfer between the mixed-valence Cu centers. We further propose a tiling model to describe how the Cu+, Cu2+, and In3+ coordination spheres can pack most favorably into a 2D perovskite lattice, which explains the unusual 1 : 2 : 1 ratio of these cations found in 1. Magnetic susceptibility data of 1 further corroborate this packing model. The emergence of enhanced visible light absorption and electronic conductivity in 1 demonstrates the importance of devising strategies for increasing the compositional complexity of halide perovskites.

Spectroscopic Definition of a Highly Reactive Site in Cu-CHA for Selective Methane Oxidation: Tuning a Mono-µ-Oxo Dicopper(II) Active Site for Reactivity.

Using UV-vis and resonance Raman spectroscopy, we identify a [Cu2O]2+ active site in O2 and N2O activated Cu-CHA that reacts with methane to form methanol at low temperature. The Cu-O-Cu angle (120°) is smaller than that for the [Cu2O]2+ core on Cu-MFI (140°), and its coordination geometry to the zeolite lattice is different. Site-selective kinetics obtained by operando UV-vis show that the [Cu2O]2+ core on Cu-CHA is more reactive than the [Cu2O]2+ site in Cu-MFI. From DFT calculations, we find that the increased reactivity of Cu-CHA is a direct reflection of the strong [Cu2OH]2+ bond formed along the H atom abstraction reaction coordinate. A systematic evaluation of these [Cu2O]2+ cores reveals that the higher O-H bond strength in Cu-CHA is due to the relative orientation of the two planes of the coordinating bidentate O-Al-O T-sites that connect the [Cu2O]2+ core to the zeolite lattice. This work along with our earlier study ( J. Am. Chem. Soc, 2018, 140, 9236-9243) elucidates how zeolite lattice constraints can influence active site reactivity.

Reversible modulation of the redox characteristics of acid-sensitive molybdenum and tungsten scorpionate complexes.

The large-scale synthesis of the scorpionate ligand Ttz (hydrotris(1,2,4-triazol-1-yl)borate) is reported as well as syntheses of Group VI complexes K[M(L)(CO)3] and M(L)(NO)(CO)2 (L = Ttz or Tp (hydrotris(pyrazol-1-yl)borate), M = Mo or W). The redox characteristics of the metal in these Ttz complexes are shown to be reversibly modulated by interactions between the exo-4-N lone pairs of the triazolyl rings and Brønsted or Lewis acids. The basicity of the scorpionate ligand in [M(Ttz)(CO)3]- is quantified (pKaH2O values range from 1.1 to 4.6) and found to be dependent on both the oxidation state and identity of the metal. In the presence of Brønsted acids, the observed redox behavior for the one-electron oxidation of the Group VI metal center is consistent with a proton-coupled electron transfer (PCET). Indeed, for both Mo and W derivatives, a one-electron oxidation decreases the pKa by ∼3.5 units.