CuII Sites Research Articles

Oriented PolyMOFs Enabled by Bridging Coligand for CO2 Separation.

Despite enormous research efforts in recent years, polymer-metal-organic framework (polyMOF) development still faces several drawbacks, such as the substantial decrease in surface area, poor crystallinity, and monophyletic chemical structure of polyMOFs. Herein, we overcome the constraints of the coordination mode of conventional polyMOFs and report a bridging coligand strategy to prepare new types of polyMOFs, where the MOFs featuring accessible CuII sites are compelled to orientally regrow within the confined channels of semirigid PIM-1 in dimethyl sulfoxide. Coordination-substitution characteristics and solvent-modulated synthesis enable the Cu centers in MOFs to coordinate with the N atoms from PIM-1 by bridging coligand mode. The reduced particle size, enhanced ultramicroporosity, preferential orientation, and superior filler-matrix compatibility endow the polyMOF-based mixed matrix membrane with excellent CO2 separation performance, with a CO2 permeability of 4669 Barrer, and with a CO2/N2 selectivity of ∼30. This polyMOF design concept exploits a viable avenue for developing more inorganic-organic hybrid materials.

Oriented 1D Metal-Organic Frameworks for Selective Chemisorption by a Substitution-Insertion Mechanism.

Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and purification of targeted systems. Herein, oriented 1D NH2-CuBDC·H2O metal-organic frameworks (MOFs) featuring accessible CuII sites are successfully fabricated by bottom-up interfacial polymerization. The prepared MOFs, as deliberately self-assembled secondary particles, exhibit a visually detectable coordination-responsive characteristic induced by the nucleophilic substitution and competitive coordination of guest molecules. As a versatile phase-change chemosorbent, the MOFs exhibit unprecedented NH3 capture (18.83 mmol g-1 at 298 K) and bioethanol dehydration performance (enriching ethanol from 99% to 99.99% within 10 min by direct adsorption separation of liquid mixtures of ethanol and water). Furthermore, the raw materials for preparing the 1D MOFs are inexpensive and readily available, and the facile regeneration with water washing at room temperature effectively minimizes the energy consumption and cost of recycling, enabling it to be the most valuable adsorbent for the removal and separation of target substances.

Geometric Tuning of Coordinatively Unsaturated Copper(I) Sites in Metal-Organic Frameworks for Ambient-Temperature Hydrogen Storage.

Porous solids can accommodate and release molecular hydrogen readily, making them attractive for minimizing the energy requirements for hydrogen storage relative to physical storage systems. However, H2 adsorption enthalpies in such materials are generally weak (-3 to -7 kJ/mol), lowering capacities at ambient temperature. Metal-organic frameworks with well-defined structures and synthetic modularity could allow for tuning adsorbent-H2 interactions for ambient-temperature storage. Recently, Cu2.2Zn2.8Cl1.8(btdd)3 (H2btdd = bis(1H-1,2,3-triazolo-[4,5-b],[4',5'-i])dibenzo[1,4]dioxin; CuI-MFU-4l) was reported to show a large H2 adsorption enthalpy of -32 kJ/mol owing to π-backbonding from CuI to H2, exceeding the optimal binding strength for ambient-temperature storage (-15 to -25 kJ/mol). Toward realizing optimal H2 binding, we sought to modulate the π-backbonding interactions by tuning the pyramidal geometry of the trigonal CuI sites. A series of isostructural frameworks, Cu2.7M2.3X1.3(btdd)3 (M = Mn, Cd; X = Cl, I; CuIM-MFU-4l), was synthesized through postsynthetic modification of the corresponding materials M5X4(btdd)3 (M = Mn, Cd; X = CH3CO2, I). This strategy adjusts the H2 adsorption enthalpy at the CuI sites according to the ionic radius of the central metal ion of the pentanuclear cluster node, leading to -33 kJ/mol for M = ZnII (0.74 Å), -27 kJ/mol for M = MnII (0.83 Å), and -23 kJ/mol for M = CdII (0.95 Å). Thus, CuICd-MFU-4l provides a second, more stable example of optimal H2 binding energy for ambient-temperature storage among reported metal-organic frameworks. Structural, computational, and spectroscopic studies indicate that a larger central metal planarizes trigonal CuI sites, weakening the π-backbonding to H2.

Confined CuⅠ sites in partially electro-reduced 2D conductive Cu-MOF film for boosting CO2 electrocatalysis to C2 products

Cu-based catalysts, especially co-sites of Cu0 and CuⅠ, are the best competitors for electrochemical CO2 fixation to produce multi-carbon (C2 + ) products. However, it is challenging to construct highly stable CuⅠ sites due to the changeability of its valence state and electronic structure in the electroreduction process, and the mechanism is also elusive. Herein, a 2D conductive CuⅡ-MOF film (CuⅡHHTP@Cu0) is prepared on Cu (100) foil by in-situ electrochemical assembly. After pre-reduction, the in-situ produced Cu2O clusters are confined in the cavities of the film created by the local breaking of the MOF framework to construct a unique CuⅠ-CuⅡHHTP@Cu0 catalyst, so that a novel strategy is proposed to stablize highly dispersed CuⅠ sites during electrochemical reduction, thus protecting the Cu2O clusters from further reduction and ensuring the coexistence of CuⅠ (111)-Cu0 (100) sites. As such, the current density of CO2 electrochemical reduction catalyzed by this catalyst exceeds 300 mA cm−2, the duration overs 50 h, and the C2 selectivity achieves 72.6 %. In-situ spectroscopy and theoretical calculations reveal that the optimized microenvironment of the CuⅠ (111) sites reduces the energy barrier of *OCCOH coupling, and Cu0 (100) sites increase the coverage of *CO, thus boosting the production of C2 products.

Cyclable CuⅠ-Ov-Mn sites accelerate O2 activation to enhance photo-driven catalytic oxidation performance

Molecular oxygen activation (MOA) plays a crucial function in various oxidation reactions. Nonetheless, facile, continuous and efficient MOA remains challenging. Herein, we have successfully constructed recyclable CuⅠ-Ov-Mn sites (Ov: oxygen vacancy) for MOA by incorporating Cu single atoms in MnO2 matrix. The localized photogenerated electron at CuⅡ site drives the generation of electron-rich CuⅠ species and an adjacent photoinduced Ov, which possesses stronger O2 affinity and affords a durable O2 activation site. The CuⅡ/CuⅠ cycle accelerates the separation of charge carriers to supply adequate photogenerated electrons and assures the renewability of photoinduced Ov, thus realizing rapid and sustained O2 activation and generating abundant monatomic oxygen ions (O-). Consequently, Cu-MnO2 catalyst performed extraordinarily high activity in O2-involved reactions. For instance, in toluene oxidation, toluene conversion reached as high as 96 %, comparable to that on the state-of-the-art supported Pt catalysts. This work will bring more possibilities for modulating the O2-involved oxidative reactions.

HYSCORE and QM/MM Studies of Second Sphere Variants of the Type 1 Copper Site in Azurin: Influence of Mutations on the Hyperfine Couplings of Remote Nitrogens.

Secondary coordination sphere (SCS) interactions have been shown to play important roles in tuning reduction potentials and electron transfer (ET) properties of the Type 1 copper proteins, but the precise roles of these interactions are not fully understood. In this work, we examined the influence of F114P, F114N, and N47S mutations in the SCS on the electronic structure of the T1 copper center in azurin (Az) by studying the hyperfine couplings of (i) histidine remote Nε nitrogens and (ii) the amide Np using the two-dimensional (2D) pulsed electron paramagnetic resonance (EPR) technique HYSCORE (hyperfine sublevel correlation) combined with quantum mechanics/molecular mechanics (QM/MM) and DLPNO-CCSD calculations. Our data show that some components of hyperfine tensor and isotropic coupling in N47SAz and F114PAz (but not F114NAz) deviate by up to ∼±20% from WTAz, indicating that these mutations significantly influence the spin density distribution between the CuII site and coordinating ligands. Furthermore, our calculations support the assignment of Np to the backbone amide of residue 47 (both in Asn and Ser variants). Since the spin density distributions play an important role in tuning the covalency of the Cu-Scys bond of Type 1 copper center that has been shown to be crucial in controlling the reduction potentials, this study provides additional insights into the electron spin factor in tuning the reduction potentials and ET properties.

Selective CO2 Photoreduction Enabled by Water-stable Cu-based Metal-organic Framework Nanoribbons.

The goal of photocatalytic CO2 reduction system is to achieve near 100 % selectivity for the desirable product with reasonably high yield and stability. Here, two-dimensional metal-organic frameworks are constructed with abundant and uniform monometallic active sites, aiming to be an emerged platform for efficient and selective CO2 reduction. As an example, water-stable Cu-based metal-organic framework nanoribbons with coordinatively unsaturated single CuII sites are first fabricated, evidenced by X-ray diffraction patterns and X-ray absorption spectroscopy. In situ Fourier-transform infrared spectra and Gibbs free energy calculations unravel the formation of the key intermediate COOH* and CO* is an exothermic and spontaneous process, whereas the competitive hydrogen evolution reaction is endothermic and non-spontaneous, which accounts for the selective CO2 reduction. As a result, in an aqueous solution containing 1 mol L-1 KHCO3 and without any sacrifice reagent, the water-stable Cu-based metal-organic framework nanoribbons exhibited an average CO yield of 82 μmol g-1 h-1 with the selectivity up to 97 % during 72 h cycling test, which is comparable to other reported photocatalysts under similar conditions.

Selective Adsorption of Oxygen from Humid Air in a Metal-Organic Framework with Trigonal Pyramidal Copper(I) Sites.

High or enriched-purity O2 is used in numerous industries and is predominantly produced from the cryogenic distillation of air, an extremely capital- and energy-intensive process. There is significant interest in the development of new approaches for O2-selective air separations, including the use of metal-organic frameworks featuring coordinatively unsaturated metal sites that can selectively bind O2 over N2 via electron transfer. However, most of these materials exhibit appreciable and/or reversible O2 uptake only at low temperatures, and their open metal sites are also potential strong binding sites for the water present in air. Here, we study the framework CuI-MFU-4l (CuxZn5-xCl4-x(btdd)3; H2btdd = bis(1H-1,2,3-triazolo[4,5-b],[4',5'-i])dibenzo[1,4]dioxin), which binds O2 reversibly at ambient temperature. We develop an optimized synthesis for the material to access a high density of trigonal pyramidal CuI sites, and we show that this material reversibly captures O2 from air at 25 °C, even in the presence of water. When exposed to air up to 100% relative humidity, CuI-MFU-4l retains a constant O2 capacity over the course of repeated cycling under dynamic breakthrough conditions. While this material simultaneously adsorbs N2, differences in O2 and N2 desorption kinetics allow for the isolation of high-purity O2 (>99%) under relatively mild regeneration conditions. Spectroscopic, magnetic, and computational analyses reveal that O2 binds to the copper(I) sites to form copper(II)-superoxide moieties that exhibit temperature-dependent side-on and end-on binding modes. Overall, these results suggest that CuI-MFU-4l is a promising material for the separation of O2 from ambient air, even without dehumidification.

Surface Structure to Tailor the Electrochemical Behavior of Mixed-Valence Copper Sulfides during Water Electrolysis.

The semiconducting behavior of mixed-valence copper sulfides arises from the pronounced covalency of Cu-S bonds and the exchange coupling between CuI and CuII centers. Although electrocatalytic study with digenite Cu9S5 and covellite CuS has been performed earlier, detailed redox chemistry and its interpretation through lattice structure analysis have never been realized. Herein, nanostructured Cu9S5 and CuS are prepared and used as electrode materials to study their electrochemistry. Powder X-ray diffraction (PXRD) and microscopic studies have found the exposed surface of Cu9S5 to be d(0015) and d(002) for CuS. Tetrahedral (Td) CuII, distorted octahedral (Oh) CuII, and trigonal planar (Tp) CuI sites form the d(0015) surface of Cu9S5, while the (002) surface of CuS consists of only Td CuII. The distribution of CuI and CuII sites in the lattice, predicted by PXRD, can further be validated through core-level Cu 2p X-ray photoelectron spectroscopy (XPS). The difference in the electrochemical response of Cu9S5 and CuS arises predominantly from the different copper sites present in the exposed surfaces and their redox states. In situ Raman spectra recorded during cyclic voltammetric study indicates that Cu9S5 is more electrochemically labile compared to CuS and transforms rapidly to CuO/Cu2O. Contact-angle and BET analyses imply that a high-surface-energy and macroporous Cu9S5 surface favors the electrolyte diffusion, which leads to a pronounced redox response. Post-chronoamperometric (CA) characterizations identify the potential-dependent structural transformation of Cu9S5 and CuS to CuO/Cu2O/Cu(OH)2 electroactive species. The performance of the in situ formed copper-oxides towards electrocatalytic water-splitting is superior compared to the pristine copper sulfides. In this study, the redox chemistry of the Cu9S5/CuS has been correlated to the atomic arrangements and coordination geometry of the surface exposed sites. The structure-activity correlation provides in-depth knowledge of how to interpret the electrochemistry of metal sulfides and their in situ potential-driven surface/bulk transformation pathway to evolve the active phase.

Thiacalix[4]arene-protected mixed-valent Ti-CuICuII clusters for electrocatalytic CO2 reduction

Two mixed-valent Ti-CuICuII clusters, Ti1Cu4 and Ti2Cu5, with different exposed CuI sites were synthesized by selecting 4-tert-Butylthiacalix[4]arene (H4TC4A) as an organic protective ligand. Electrocatalytic CO2 reduction reactions (CO2RR) studies indicate main HCOOH production for Ti1Cu4, and improved CH4 and CO production for Ti2Cu5.

Constructing copper-organic framework with exceptionally high volumetric working capacity for efficient methane storage

Extensive efforts have been devoted to developing novel porous structures for methane storage with high volumetric uptake and volumetric working capacity. In this study, a NbO-type copper–organic framework (CMOF-1) was designed and synthesized. Notably, the CMOF-1 posses suitable nanocages decorated with carboxylate groups and nitrogen sites, exhibiting a remarkable volumetric uptake of 260 cm3 cm−3 (at 65 bar/298 K) and a volumetric working capacity of 202 cm3 cm−3 (from 5 to 65 bar). These values are comparable to those of the benchmark material HKUST-1 (267 cm3 cm−3 and 190 cm3 cm−3) and exceed those of the structural analogue ZJU-5a (249 cm3 cm−3 and 188 cm3 cm−3) under the same conditions. The grand canonical Monte Carlo simulations and density functional theory calculations reveal that the high methane volumetric uptake might be contributed by the open CuII sites and nanocages with suitable sizes/shapes and functional sites, which can enforce strong gas-framework and gas–gas interactions. The methodology presented in this work should envision potential practical applications in methane storage and could be generalized to design other novel materials for the storage of other gases like hydrogen.

Nitrite and Nitric Oxide Interconversion at Mononuclear Copper(II): Insight into the Role of the Red Copper Site in Denitrification.

Nitrite (NO2 - ) and nitric oxide (NO) interconversion is crucial for maintaining optimum NO flux in mammalian physiology. Herein we demonstrate that [L2 CuII (nitrite)]+ moieties (in 2 a and 2 b; where, L = Me2 PzPy and Me2 PzQu) with distorted octahedral geometry undergo facile reduction to provide tetrahedral [L2 CuI ]+ (in 3 a and 3 b) and NO in the presence of biologically relevant reductants, such as 4-methoxy-2,6-di-tert-butylphenol (4-MeO-2,6-DTBP, a tyrosine model) and N-benzyl-1,4-dihydronicotinamide (BNAH, a NAD(P)H model). Interestingly, the reaction of excess NO gas with [L2 CuII (MeCN)2 ]2+ (in 1 a) provides a putative {CuNO}10 species, which is effective in mediating the nitrosation of various nucleophiles, such as thiol and amine. Generation of the transient {CuNO}10 species in wet acetonitrile leads to NO2 - as assessed by Griess assay and 14 N/15 N-FTIR analyses. A detailed study reveals that the bidirectional NOx -reactivity, namely, nitrite reductase (NIR) and NO oxidase (NOO), at a common CuII site, is governed by the geometric-preference-driven facile CuII /CuI redox process. Of broader interest, this study not only highlights potential strategies for the design of copper-based catalysts for nitrite reduction, but also strengthens the previous postulates regarding the involvement of red copper proteins in denitrification.

Nitrite and Nitric Oxide Interconversion at Mononuclear Copper(II): Insight into the Role of the Red Copper Site in Denitrification

AbstractNitrite (NO2−) and nitric oxide (NO) interconversion is crucial for maintaining optimum NO flux in mammalian physiology. Herein we demonstrate that [L2CuII(nitrite)]+ moieties (in 2 a and 2 b; where, L = Me2PzPy and Me2PzQu) with distorted octahedral geometry undergo facile reduction to provide tetrahedral [L2CuI]+ (in 3 a and 3 b) and NO in the presence of biologically relevant reductants, such as 4‐methoxy‐2,6‐di‐tert‐butylphenol (4‐MeO‐2,6‐DTBP, a tyrosine model) and N‐benzyl‐1,4‐dihydronicotinamide (BNAH, a NAD(P)H model). Interestingly, the reaction of excess NO gas with [L2CuII(MeCN)2]2+ (in 1 a) provides a putative {CuNO}10 species, which is effective in mediating the nitrosation of various nucleophiles, such as thiol and amine. Generation of the transient {CuNO}10 species in wet acetonitrile leads to NO2− as assessed by Griess assay and 14N/15N‐FTIR analyses. A detailed study reveals that the bidirectional NOx‐reactivity, namely, nitrite reductase (NIR) and NO oxidase (NOO), at a common CuII site, is governed by the geometric‐preference‐driven facile CuII/CuI redox process. Of broader interest, this study not only highlights potential strategies for the design of copper‐based catalysts for nitrite reduction, but also strengthens the previous postulates regarding the involvement of red copper proteins in denitrification.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper‐Containing Mordenite: Insights into Reaction Mechanism and Product Protection

AbstractCopper(II)‐containing mordenite (CuMOR) is capable of activation of C−H bonds in C1‐C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time‐resolved Cu K‐edge X‐ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π‐complexes of olefins with CuI sites, formed upon reduction of CuII‐oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Selective Oxidative Dehydrogenation of Ethane and Propane over Copper-Containing Mordenite: Insights into Reaction Mechanism and Product Protection.

Copper(II)-containing mordenite (CuMOR) is capable of activation of C-H bonds in C1 -C3 alkanes, albeit there are remarkable differences between the functionalization of ethane and propane compared to methane. The reaction of ethane and propane with CuMOR results in the formation of ethylene and propylene, while the reaction of methane predominantly yields methanol and dimethyl ether. By combining in situ FTIR and MAS NMR spectroscopies as well as time-resolved Cu K-edge X-ray absorption spectroscopy, the reaction mechanism was derived, which differs significantly for each alkane. The formation of ethylene and propylene proceeds via oxidative dehydrogenation of the corresponding alkanes with selectivity above 95 % for ethane and above 85 % for propane. The formation of stable π-complexes of olefins with CuI sites, formed upon reduction of CuII -oxo species, protects olefins from further oxidation and/or oligomerization. This is different from methane, the activation of which proceeds via oxidative hydroxylation leading to the formation of surface methoxy species bonded to the zeolite framework. Our findings constitute one of the major steps in the direct conversion of alkanes to important commodities and open a novel research direction aiming at the selective synthesis of olefins.

Revealing the Formation and Reactivity of Cage-Confined Cu Pairs in Catalytic NOx Reduction over Cu-SSZ-13 Zeolites by In Situ UV-Vis Spectroscopy and Time-Dependent DFT Calculation.

The low-temperature mechanism of chabazite-type small-pore Cu-SSZ-13 zeolite, a state-of-the-art catalyst for ammonia-assisted selective reduction (NH3-SCR) of toxic NOx pollutants from heavy-duty vehicles, remains a debate and needs to be clarified for further improvement of NH3-SCR performance. In this study, we established experimental protocols to follow the dynamic redox cycling (i.e., CuII ↔ CuI) of Cu sites in Cu-SSZ-13 during low-temperature NH3-SCR catalysis by in situ ultraviolet-visible spectroscopy and in situ infrared spectroscopy. Further integrating the in situ spectroscopic observations with time-dependent density functional theory calculations allows us to identify two cage-confined transient states, namely, the O2-bridged Cu dimers (i.e., μ-η2:η2-peroxodiamino dicopper) and the proximately paired, chemically nonbonded CuI(NH3)2 sites, and to confirm the CuI(NH3)2 pair as a precursor to the O2-bridged Cu dimer. Comparative transient experiments reveal a particularly high reactivity of the CuI(NH3)2 pairs for NO-to-N2 reduction at low temperatures. Our study demonstrates direct experimental evidence for the transient formation and high reactivity of proximately paired CuI sites under zeolite confinement and provides new insights into the monomeric-to-dimeric Cu transformation for completing the Cu redox cycle in low-temperature NH3-SCR catalysis over Cu-SSZ-13.

Single Cu sites in synergy with Cu2O nanoparticles on rutile TiO2 for selective nitroarene hydrogenation

Catalytic hydrogenation of nitroarenes plays a crucial role in industrial production of arylamines which are main building blocks in a wide range of products. Supported noble metal catalysts and group VIII transition metals are generally encapsulated or anchored to heteroatoms to achieve high selectivity. In this work, we show that, among Cu based catalysts on various supports, copper on rutile TiO2 (TiO2-R) prepared simply by direct H2 reduction without the encapsulation or heteroatom modification is remarkably active, selective, and stable for hydrogenation of nitroarenes, producing arylamines in superhigh selectivity. Essential to the catalytic performance, a unique mechanism involving indispensable Cu2O nanoparticle sites and dispersed single CuI ion sites are identified. Specifically, Cu2O nanoparticles provide essential sites for H2 dissociation, and the colony of dispersed single CuI sites play two crucial roles: (1) as step-stones for H migration, as inferred by kinetic energy experiments, and (2) nitroarene adsorption/hydrogenation sites. This work provides new insights on the nature of the Cu/TiO2-R selective hydrogenation catalyst and also elucidates a method for the identification and distinction of spatially separated active sites on metal-oxide catalysts.

Beyond surface: Correlating CuI /CuII and O-vacancy surface sites in CuxO nanocubes with their activities as noble metal-free anodes for fuel cells

Nanocrystals' surface area and shape significantly impact their activities in fuel cells. On the other hand, additional parameters that may affect their activities cannot be neglected. Here, we demonstrate that the presence of crystalline defects (such as oxygen vacancies) and the relative concentration of CuI/CuII may also vary with the decrease of CuxO nanocubes sizes, contributing to the observed activities as noble metal-free anodes for methanol fuel cells. However, such differences did not follow the size as expected, showing that this parameter does not play a critical role in determining materials' properties. To this end, CuxO nanocubes having controllable sizes (50, 65, and 85 nm) were synthesized by a simple and similar protocol, leading to nanocrystals enclosed by {100} surfaces. When the catalytic activity of the different-sized CuxO nanocubes was performed toward the electrooxidation of methanol in alkaline media, the observed performances decreased as follows: 50 nm > 85 nm > 65 nm-CuxO nanocubes, in which 50 nm-CuxO nanocubes led to the best electrocatalytic results. Interestingly, our results showed that the differences in the catalytic activities of CuxO nanocubes displaying different sizes could not only be assigned to a gain of surface area with a decrease in particle size. More specifically, XPS results indicated that the reduction of particle size led to an increase in both Os/OL and Cu(I)/Cu(II) ratios, demonstrating the enrichment of oxygen vacancies at the surface of CuxO nanocubes, which also contributed for the observed catalytic activities.

Cu+-Mediated CO Coordination for Promoting C–C Coupling for CO2 and CO Electroreduction

Selective electrochemical upgrading of CO2 to multicarbon (C2+) products requires a C-C coupling process, yet the underlying promoting mechanism of widely involved Cu oxidation states remains largely unclear, hindering the subtle design of efficient catalysts. Herein, we unveil the critical role of Cu+ in promoting C-C coupling via coordination with a CO intermediate during electrochemical CO2 reduction. We find that, relative to other halogen anions, iodide (I-) in HCO3- electrolytes accelerates the generation of strongly oxidative hydroxyl radicals that accounts for the formation of Cu+, which can be dynamically stabilized by I- via the formation of CuI. The in situ generated CO intermediate strongly binds to CuI sites, forming nonclassical Cu(CO)n+ complexes, leading to an approximately 3.0-fold increase of C2+ Faradaic efficiency at -0.9 VRHE relative to that of I--free Cu surfaces. Accordingly, a deliberate introduction of CuI into I--containing HCO3- electrolytes for direct CO electroreduction brings about a 4.3-fold higher C2+ selectivity. This work provides insights into the role of Cu+ in C-C coupling and the enhanced C2+ selectivity for CO2 and CO electrochemical reduction.

A redox model for NO oxidation, NH3 oxidation and high temperature standard SCR over Cu-SSZ-13

A kinetic model is developed to predict the influence of temperature and hydrothermal aging on the redox of active Cu sites under standard SCR, NO oxidation and NH3 oxidation conditions over a practically relevant fully-formulated Cu-SSZ-13 catalyst. NO2/N2 production during NO/NH3 titration of CuII sites is utilized to identify rate parameters associated with NO-only RHC (reduction half cycle) and NH3-only RHC respectively. Integral N2 formation during subsequent NO + NH3 titration is consistent with the production of one NO2 per two CuII sites reduced during NO-only RHC and one N2 per six CuII sites reduced during NH3-only RHC. Decreased reduction of CuII sites by NO/NH3 upon hydrothermal aging, along with the production of one NO2 per two CuII sites during NO-only RHC, is accordant with the involvement of proximal ZCuOH and oxygen-bridged dimeric CuII sites. Oxidation of partially solvated and framework coordinated ZCu (CuI) sites occurs in presence of O2, does not produce N2 and can lead to the consumption of Brønsted acid sites. A global OHC kinetic model is developed to predict transient and integral N2 formation during exposure of CuI sites to a mixture of NO and O2. The resulting redox kinetic model quantitatively predicts NO and NH3 consumption during isothermal transient response Cu redox (TRCR) protocols, along with temperature and age dependent steady-state standard SCR and oxidation conditions. The redox model presented in this work synthesizes recent kinetic, spectroscopic and computational findings to provide a foundational description of active site redox during standard SCR, NO oxidation and NH3 oxidation over Cu-SSZ-13.