Role of the nature of copper sites in the activity of copper-based catalysts for no conversion

The activities of the copper-based catalysts, Cu²⁺ /SiO²,Cu²⁺ /Vycor and Cu²⁺/ZSM-5, and V²O⁵/TiO² for NO conversion to N² in the presence or absence of NH³ and/or O² have been investigated. The Cu²⁺ /ZSM-5 catalyst exhibited the highest activity, even higher than that of V²O⁵/TiO². Photoluminescence studies of the dehydrated copper-based catalysts have suggested that the copper ions anchored onto ZSM-5 locate as isolated copper species near Brönsted sites in the zeolite channels while the copper ions anchored onto Vycor and SiO² locate mainly as copper dimer forms. These results suggest the role of copper ions which are stabilized with near-lying oxygen vacancies created by dehydroxylation of the zeolite, in NO conversion. As a result, it may be concluded that the isolated copper ions near Brönsted sites play a significant role in NO conversion but dimeric or polynuclear copper species are less effective for the reaction.     

The Properties of Cu Ions in Zeolites CuY Studied by IR Spectroscopy

The properties of both Cu²⁺ and Cu⁺ ions in zeolite CuY were followed with NO and CO as probe molecules. Cu²⁺ was found to be located in S_II, S_II*, and S_III sites, whereas Cu⁺ was found in S_II and S_II* sites. The fine analysis of the spectra of Cu²⁺-NO and Cu⁺-CO adducts suggests that both in S_II and in S_II* sites two kinds of Cu cations exist. They differ in the positive charge, which may be related to the varying numbers of AlO₄⁻ in close proximity. The experiments of NO and CO adsorption and desorption evidenced that both Cu²⁺ and Cu⁺ sites of highest positive charge bind probe molecules most strongly but activate them to a lesser extent than the Cu sites of lowest positive charge. The experiments of reduction with hydrogen evidenced that the Cu ions of higher positive charge are first reduced by hydrogen. On the other hand, Cu sites of the lowest positive charge are first oxidized by oxygen. The experiments with CuNaY zeolites of various Cu contents suggest that the first introduced Cu (at low Cu contents) created Cu⁺, which was the most neutralized by framework oxygens. Such Cu cations are the most stabilized by framework oxygens.     

Stability of Ultradisperse Copper in a Sulfo Cation Exchanger Matrix

The recrystallization of ultradisperse copper chemically deposited onto a sulfo cation exchanger matrix was studied by the potentiometric method. The stationary value of the electrode potential of the copper-sulfo cation exchanger composite was established during a long period of time, which depended on the ionic form of the composite (H⁺, Cu²⁺, or Na⁺), solution composition (CuSO₄, H₂SO₄, and Na₂SO₄), and solution concentration. Recrystallization was favored by copper(II) counterions, which entered the composite as a result of ion exchange, nonexchange absorption of copper sulfate, or preliminary composite transformation into the Cu²⁺ form. In the quasi-equilibrium state, the concentration of copper(II) counterions was maintained at a high level by the Donnan interfacial potential. At all the copper(II) sulfate concentrations used, the potential of the Cu²⁺/Cu ion—metal pair in the ion-exchange matrix remained at virtually the same level, which was indicative of the stable state of copper particles. In the absence of an external source of copper ions, recrystallization was significantly hindered; therefore, the potential exhibited only a slight drift. Copper ions formed in the solution of small crystals were localized in the vicinity of ionogenic matrix centers, which decreased the mobility of these particles as counterions; therefore, the dispersity of particles remained unchanged.     

Low-temperature activation of nitrogen oxide on Cu-ZSM-5 catalysts

The adsorption and activation of NO molecules on Cu-ZSM-5 catalysts with different Cu/Al and Si/Al ratios (from 0.05 to 1.4 and from 17 to 45, respectively) subjected to different pretreatment was studied by ultraviolet-visible diffuse reflectance (UV-Vis DR). It was found that the amount of chemisorbed NO and the catalyst activity in NO decomposition increased with an increase in the Cu/Al ratio to 0.35–0.40. The intensity of absorption bands at 18400 and 25600 cm⁻¹ in the UV-Vis DR spectra increased symbatically. It was hypothesized that the adsorption of NO occurs at Cu⁺ ions localized in chain copper oxide structures with the formation of mono- and dinitrosyl Cu(I) complexes, and this process is accompanied by the Cu²⁺...Cu⁺ intervalence transfer band in the region of 18400 cm⁻¹. The low-temperature activation of NO occurs through the conversion of the dinitrosyl Cu(I) complex into the π-radical anion (N₂O₂)⁻ stabilized at the Cu²⁺ ion of the chain structure, [Cu²⁺-cis-(N₂O₂)⁻], by electron transfer from the Cu⁺ ion to the cis dimer (NO)₂. This complex corresponds to the L → M charge transfer band in the region of 25600 cm⁻¹. The subsequent destruction of the complex [Cu²⁺-cis-(N₂O₂)⁻] at temperatures of 150–300°C leads to the release of N₂O and the formation of the complex [Cu²⁺O⁻], which further participates in the formation of the nitrite-nitrate complexes [Cu²⁺(NO₂)⁻], [Cu²⁺(NO)(NO₂)⁻], and [Cu²⁺(NO₃)⁻] and NO decomposition products.     

Dynamic photoluminescence studies of vanadium oxide anchored on SiO2 and the effects of added O2 and H2O

Dynamcc photoluminescence studies of V-ozide anchored onto SiO₂ are investigated in the absence and presence of O₂ or H₂O. It is found that the added O₂ molecules interact with the charge transfer excited triplet state of tetrahedrally coordinaeed V-oxide species. This results in an efficient quenching of the phosphorescence due to an enhanced radiationless deactivation. On the other hand, the added H₂O molecules interact with V-oxide in the ground state, resulting in the coordination change of V-species from tetrahedral to octahedral. These results obtained by dynamic photoluminescence spectroscopy are in good agreement with those obtained by ESR measurements of the photoreduced V⁴⁺ ions. From the Stern-Volmer plots for the quenching of the phosphorescence of V-oxide, the absolute quenching rate constants (reaction rate constants) of O₂ for the charge transfer excited triplet state of V-oxide anchored onto SiO₂ is first determined to be 3.2 × 10⁸ g-cat./mol s at 77 K and 9.3 × 10¹² g-cat./mol s at 298 K.     

Isolation of the Copper Redox Steps in the Standard Selective Catalytic Reduction on Cu‐SSZ‐13

Operando X‐ray absorption experiments and density functional theory (DFT) calculations are reported that elucidate the role of copper redox chemistry in the selective catalytic reduction (SCR) of NO over Cu‐exchanged SSZ‐13. Catalysts prepared to contain only isolated, exchanged Cu^II ions evidence both Cu^II and Cu^I ions under standard SCR conditions at 473 K. Reactant cutoff experiments show that NO and NH₃ together are necessary for Cu^II reduction to Cu^I. DFT calculations show that NO‐assisted NH₃ dissociation is both energetically favorable and accounts for the observed Cu^II reduction. The calculations predict in situ generation of Brønsted sites proximal to Cu^I upon reduction, which we quantify in separate titration experiments. Both NO and O₂ are necessary for oxidation of Cu^I to Cu^II, which DFT suggests to occur by a NO₂ intermediate. Reaction of Cu‐bound NO₂ with proximal NH₄⁺ completes the catalytic cycle. N₂ is produced in both reduction and oxidation half‐cycles.     

Evidence for long-lived excited states of [CnH2]2+ carbodications

The energetics, structures, stabilities and reactivities of[C_nH₂]²⁺ ions have been investigated using computational methods and experimental mass spectrometric techniques. Spontaneous decompositions of [C_nH₂]²⁺ into [C_nH]⁺ + H⁺ products, observed for ions with odd-n values, have been explained by invoking the formation of excited triplet states. Even-n [C_nH]⁺ ions possess triplet ground states with low-lying excited states, whereas odd-n ions have triplet states with energies several eV above ground singlet states. Radiationless transitions of vibrationally excited long-lived triplet state ions into singlet state continua are suggested as possible mechanisms for spontaneous deprotonation processes of odd-n [C_nH₂]²⁺ ions. Evidence for these long-lived excited states has been obtained in bimolecular single electron transfer reactions.     

Zeolite ZSM-5 containing copper ions: The effect of the copper salt anion and NH<Subscript>4</Subscript>OH/Cu<Superscript>2+</Superscript> ratio on the state of the copper ions and on the reactivity of the zeolite in DeNO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Isotherms of copper cation sorption by H-ZSM-5 zeolite from aqueous and aqueous ammonia solutions of copper acetate, chloride, nitrate, and sulfate are considered in terms of Langmuir’s monomolecular adsorption model. Using UV-Vis diffuse reflectance spectroscopy, IR spectroscopy, and temperatureprogrammed reduction with hydrogen and carbon monoxide, it has been demonstrated that the electronic state of the copper ions is determined by the ion exchange and heat treatment conditions. The state of the copper ions has an effect on the redox properties and reactivity of the Cu-ZSM-5 catalysts in the selective catalytic reduction (SCR) of NO with propane and in N₂O decomposition. The amount of Cu²⁺ that is sorbed by zeolite H-ZSM-5 from aqueous solution and is stabilized as isolated Cu²⁺ cations in cationexchange sites of the zeolite depends largely on the copper salt anion. The quantity of Cu(II) cations sorbed from aqueous solutions of copper salts of strong acids is smaller than the quantity of the same cations sorbed from the copper acetate solution. When copper chloride or sulfate is used, the zeolite is modified by the chloride or sulfate anion. Because of the presence of these anions, the redox properties and nitrogen oxides removal (DeNO _x ) efficiency of the Cu-ZSM-5 catalysts prepared using the copper salts of strong acids are worse than the same characteristics of the sample prepared using the copper acetate solution. The addition of ammonia to the aqueous solutions of copper salts diminishes the copper salt anion effect on the amount of Cu(II) sorbed from these solutions and hampers the nonspecific sorption of anions on the zeolite surface. As a consequence, the redox and DeNO _x properties of Cu-ZSM-5 depend considerably on the NH₄OH/Cu²⁺ ratio in the solution used in ion exchange. The aqueous ammonia solutions of the copper salts with NH₄OH/Cu²⁺ = 6–10 stabilize, in the Cu-ZSM-5 structure, Cu²⁺ ions bonded with extraframework oxygen, which are more active in DeNO _x than isolated Cu²⁺ ions (which form at NH4OH/Cu2+ = 30) or nanosized CuO particles (which form at NH₄OH/Cu²⁺ = 3).     

Binuclear copper complexes with non-steroidal anti-inflammatory drugs as studied by electrospray ionization mass spectrometry

The solutions containing one of the copper salts (CuCl₂, Cu(ClO₄)₂, Cu(NO₃)₂, and CuSO₄) and one of the non-steroidal anti-inflammatory drugs (NSAIDs, ibuprofen, ketoprofen or naproxen) were analyzed by electrospray ionization mass spectrometry. Three of the salts, namely CuCl₂, Cu(ClO₄)₂ and Cu(NO₃)₂, yielded binuclear complexes of drug:metal stoichiometry 1:2. Existence of the complexes of such stoichiometry has not been earlier observed. For copper(II) chloride the complexes (ions of the type [M-HCOOH+Cu₂Cl]⁺ and [M+Cu₂Cl]⁺, M stands for the drug molecule) were formed in the gas phase. When copper(II) perchlorate or copper(II) nitrate was used, the observed binuclear copper complexes (ions of the type [M-H+Cu₂(ClO₄)₂+CH₃OH]⁺, [M-H+Cu₂(ClO₄)₂]⁺ and [M-H+Cu₂(NO₃)₂+CH₃OH]⁺, [M-H+Cu₂(NO₃)₂]⁺) were observed at low cone voltage, thus these complexes must have already existed in the solution analysed. Therefore, such complexes may also exist under physiological conditions.      

UV/Vis Spectroscopy of Copper Formate Clusters: Insight into Metal-Ligand Photochemistry

The electronic structure and photochemistry of copper formate clusters, Cu^I₂(HCO₂)₃⁻ and Cu^II_n(HCO₂)_2n+1⁻, n≤8, are investigated in the gas phase by using UV/Vis spectroscopy in combination with quantum chemical calculations. A clear difference in the spectra of clusters with Cu^I and Cu^II copper ions is observed. For the Cu^I species, transitions between copper d and s/p orbitals are recorded. For stoichiometric Cu^II formate clusters, the spectra are dominated by copper d–d transitions and charge-transfer excitations from formate to the vacant copper d orbital. Calculations reveal the existence of several energetically low-lying isomers, and the energetic position of the electronic transitions depends strongly on the specific isomer. The oxidation state of the copper centers governs the photochemistry. In Cu^II(HCO₂)₃⁻, fast internal conversion into the electronic ground state is observed, leading to statistical dissociation; for charge-transfer excitations, specific excited-state reaction channels are observed in addition, such as formyloxyl radical loss. In Cu^I₂(HCO₂)₃⁻, the system relaxes to a local minimum on an excited-state potential-energy surface and might undergo fluorescence or reach a conical intersection to the ground state; in both cases, this provides substantial energy for statistical decomposition. Alternatively, a Cu^II(HCO₂)₃Cu⁰⁻ biradical structure is formed in the excited state, which gives rise to the photochemical loss of a neutral copper atom.     

Cu2+-Anchored Carbon Nano-Photocatalysts for Visible Water Splitting to Boost Hydrogen Cuproptosis

Both hydrogen (H₂) and copper ions (Cu⁺) can be used as anti-cancer treatments. However, the continuous generation of H₂ molecules and Cu⁺ in specific sites of tumors is challenging. Here we anchored Cu²⁺ on carbon photocatalyst (Cu@CDCN) to allow the continuous generation of H₂ and hydrogen peroxide (H₂O₂) in tumors using the two-electron process of visible water splitting. The photocatalytic process also generated redox-active Cu-carbon centers. Meanwhile, the Cu²⁺ residues reacted with H₂O₂ (the obstacle to the photocatalytic process) to accelerate the two-electron process of water splitting and cuprous ion (Cu⁺) generation, in which the Cu²⁺ residue promoted a pro-oxidant effect with glutathione through metal-reducing actions. Both H₂ and Cu⁺ induced mitochondrial dysfunction and intracellular redox homeostasis destruction, which enabled hydrogen therapy and cuproptosis to inhibit cancer cell growth and suppress tumor growth. Our research is the first attempt to integrate hydrogen therapy and cuproptosis using metal-enhanced visible solar water splitting in nanomedicine, which may provide a safe and effective cancer treatment.     

Thermoemission of singlet oxygen and chemical structure of copper oxides

Thermal treatment of copper oxides (CuO, Cu₂O) is accompanied by large-scale emission of singlet oxygen molecules (¹Σ⁺ _g ). Electron spectroscopy for chemical analysis (ESCA) and electronic and IR spectroscopy were used to show that the thermoemission of electronically excited molecules results from dark generation of electronically excited states which contain in their structure isolated metal-metal bonds and oxygen associates. The anomalous diamagnetic response of the samples and reduced thermoemission activity (Cu₂O) are associated with cooperative interaction of electronically excited states.     

Cu-loaded dealuminated Y zeolites active in selective catalytic reduction of nitric oxide with ammonia

The selective catalytic reduction of NO with ammonia in the presence of oxygen has been carried out on Cu-loaded dealuminated Y zeolite catalysts. Copper was introduced by the usual ion-exchange procedure with an aqueous solution of cupric acetate. On deeply dealuminated USY zeolites, Cu²⁺ was supported in the amount larger than 2Cu/Al=2, resulting in the formation of CuO fine particles in addition to the isolated and dimer Cu²⁺ species. The specific catalytic activity per surface copper on the CuO particles was very high compared with these Cu²⁺ species. NO adsorption measurement revealed the higher dispersion of CuO on the deeply dealuminated USY than on SiO₂, which made Cu/USY a better catalyst for the reduction of NO. The reaction intermediates were investigated through the IR spectra of adsorbed species.     

Cu-loaded dealuminated Y zeolites active in selective catalytic reduction of nitric oxide with ammonia

The selective catalytic reduction of NO with ammonia in the presence of oxygen has been carried out on Cu-loaded dealuminated Y zeolite catalysts. Copper was introduced by the usual ion-exchange procedure with an aqueous solution of cupric acetate. On deeply dealuminated USY zeolites, Cu²⁺ was supported in the amount larger than 2Cu/Al = 2, resulting in the formation of CuO fine particles in addition to the isolated and dimer Cu²⁺ species. The specific catalytic activity per surface copper on the CuO particles was very high compared with these Cu²⁺ species. NO adsorption measurement revealed the higher dispersion of CuO on the deeply dealuminated USY than on SiO₂, which made Cu/USY a better catalyst for the reduction of NO. The reaction intermediates were investigated through the IR spectra of adsorbed species.     

Theoretical and Experimental Study of Complex Ions from Reactions of Al+ (Cu+) with Amine Molecules

The gas phase reactions of metal ions (Al⁺, Cu⁺) with amine molecules [CH₃NH₂=MA, (CH₃)₂NH=DMA] were investigated using a laser ablation‐molecular beam method. The directly associated product complex ions,Al⁺‐MA and Al⁺‐DMA, and the dehydrogenation product ions, Cu⁺(CH₂NH) and Cu⁺(C₂H₅N), as well as hydrated ion Cu⁺(NC₂H₅·H₂O), have been obtained and recorded from the reactions of the metal ions and organic amine molecules, and density functional theory (B3LYP) calculations have been performed to reveal the optimized geometry, energetics, and reaction mechanism of the title reactions with basis set 6‐311+G(d,p) adopted.     

A new copper containing MALDI matrix that yields high abundances of [Peptide + Cu]+ ions

The dinuclear copper complex (α-cyano-4-hydroxycinnamic acid (CHCA) copper salt (CHCA)₄Cu₂), synthesized by reacting CHCA with copper oxide (CuO), yields increased abundances of [M + xCu − (x−1)H]⁺ (x = 1–6) ions when used as a matrix for matrix-assisted laser desorption ionization (355 nm Nd:YAG laser). The yield of [M + xCu − (x−1)H]⁺ (x = 1∼6) ion is much greater than that obtained by mixing peptides with copper salts or directly depositing peptides onto oxidized copper surfaces. The increased ion yields for [M + xCu − (x−1)H]⁺ facilitate studies of biologically important copper binding peptides. For example, using this matrix we have investigated site-specific copper binding of several peptides using fragmentation chemistry of [M + Cu]⁺ and [M + 2Cu − H]⁺ ions. The fragmentation studies reveal interesting insight on Cu binding preferences for basic amino acids. Most notable is the fact that the binding of a single Cu⁺ ion and two Cu⁺ ions are quite different, and these differences are explained in terms of intramolecular interactions of the peptide-Cu ionic complex.     

The State of Copper Ions in Aqueous and Aqueous Ammonia Solutions of Copper Acetate

Stabilization of Cu²⁺ ions in aqueous and aqueous ammonia solutions of copper acetate was studied for a wide range of ammonia concentrations. The structure of copper acetate hydrate complexes was shown to markedly change upon dissolution in water. In aqueous solutions, copper is stabilized as strongly bound Cu²⁺ associates (dimers) in a distorted octahedral environment composed of water molecules and acetate groups oxygen atoms in equatorial positions with strong exchange interaction via acetate groups. In solutions of copper acetate in aqueous ammonia, the concentration of ammonia has a crucial effect on the ordering of Cu²⁺ ions in associates. At high ammonia concentration, disordered copper tetra-ammoniate associates with the \({d_{{x^2} - {y^2}}}\) ground state are formed, whereas at low ammonia concentration, bulky Cu²⁺ ion associate structures are generated, with the \({d_{{x^2} - {y^2}}}\) ground state, hydroxyl groups in the equatorial plane, and water molecules in the axial positions.     

Electrochemical determination of standard thermodynamic parameters characterizing resolvation of Cu2+ cations in water-acetone mixtures

Standard thermodynamic parameters characterizing the resolvation of the Cu²⁺ ions and the surface potential at the gas-phase/acetone interface, Δχ^Me ₂ ^CO, are determined on the basis of the results of measuring compensating voltages of the Volta circuits by the Kenrick method at 298.15 K and the value of the surface potential at the nonaqueous-solvent/gas phase interface, Δχ _H2O ^S , which was obtained earlier. A comparison of thermodynamic parameters characterizing the resolvation of the copper ions with similar quantities for the calcium and cadmium ions is performed. Specific features pertaining to the solvation of copper ions in a mixed water-acetone solvent are elucidated and the effect of the composition and nature of the mixed solvent on the quantities obtained is determined. A dependence of variations in the thermodynamic parameters characterizing the resolvation of cations on their charge and crystallographic radius is established. The dependence corresponds to the series K⁺, Ca²⁺, Cd²⁺, Cu²⁺.     

A Photoluminescent Copper(I) Complex with an Exceptionally High CuII/CuI Redox Potential: [Cu(bfp)2]+ (bfp=2,9-bis(trifluoromethyl)-1,10-phenanthroline)

Unprecedented stabilization of the copper(I ) oxidation state is demonstrated for the complex cation [Cu(bfp)₂]⁺ ( 1 ) due to the steric and electronic effects of the CF₃ groups (E_1/2(Cu^II/Cu^I)=+1.55 V vs. SCE). The redox existence range of the copper(I ) species is remarkably high at 2.77 V. It is emissive in solution at room temperature and shows great potential as a photocatalyst; in the excited state it is a very potent photooxidant.     

Distribution and properties of catalytically active Cu2+ sites in mesoporous MCM-41 modified with Al, Zr, or W ions

The surface of pure mesoporous SiO₂ with an MCM-41 structure has been modified by introducing Al, Zr, or W ions (1 mmol/g). The original and modified materials have been loaded with Cu²⁺ ions. The distribution, properties, and thermal stability of different Cu²⁺ sites have been studied by EPR and IR spectroscopy. The resulting catalysts have been tested for activity in ethane oxidation. The modification of original MCM-41 exerts a very strong effect on the stability of isolated Cu²⁺ ions on the support surface. Among the modified supports, Al-MCM-41 affords the highest thermal stability and degree of dispersion (70–80%) of the copper-containing phase. There is no correlation between the total number of surface Cu²⁺ sites and the catalytic activity. The specific catalytic activity (per Cu²⁺ ion accessible to the reactants) depends strongly on the local structure of the sites. The isolated pentacoordinated Cu²⁺ sites stabilized by the Al-MCM-41 surface show a comparatively high activity in the sample calcined at 520°C. The heat treatment of Cu/Al-MCM-41 at 650–750°C reduces the specific activity of the catalytic sites by a factor of ～20 without sintering the copper phase, as in the case of CuHZSM-5 zeolite. The least dispersed copper phase, which is observed in the original MCM-41 and likely consists of aggregates of weakly interacting Cu²⁺ ions, exhibits the highest specific activity and thermal stability. In the case of Cu/W-MCM-41, heat treatment causes both the sintering of copper particles and a decrease in the specific activity of the surface Cu²⁺ ions.