Copper Species Research Articles

Effect of Cu loading on the performance and kinetics of Cu/SAPO-34 catalysts for selective catalytic reduction with NH3

A series of X%Cu/SAPO-34 (X = 1.0, 2.0, 4.0 and 6.0) catalysts were prepared by ultrasonic impregnation method for selective catalytic reduction (SCR) of NOx with ammonia. The effect of different Cu loadings on the selective catalytic reduction of NO by molecular sieve catalysts was examined on a fixed-bed reactor. Catalyst physicochemical properties were characterized and analyzed using XRD, TEM, NH3-TPD, H2-TPR, and in situ DRIFTS. Catalysts were used in reaction kinetics studies from the perspective of transient and steady-state kinetics. Cu/SAPO-34 catalyst with 4% Cu loading had the best denitrification efficiency and wide activity window. Copper species were highly dispersed on the catalyst surface. Cu/SAPO-34 catalyst with 4% Cu loading had rich acidic sites and excellent redox performance. Cu/SAPO-34 catalysts with 4% Cu loading possess minimal activation energy and were lower than commercial catalysts. According to the results of in situ IR, transient and steady-state analysis, the Cu/SAPO-34 catalyst with 4% Cu loading in the NH3-SCR reaction process was mainly E-R mechanism, and there was L-H mechanism.

Copper-Catalyzed Enantioselective Borylative Allyl-Allyl Coupling of Allenes and Allylic gem-Dichlorides.

A catalytic asymmetric reaction between allenes, bis(pinacolato)diboron, and allylic gem-dichlorides is reported. The method involves the coupling of a catalytically generated allyl copper species with the allylic gem-dichloride and provides chiral internal 1,5-dienes featuring (Z)-configured alkenyl boronate and alkenyl chloride units with high levels of chemo-, regio-, enantio-, and diastereoselectivity. The synthetic utility of the products is demonstrated with the synthesis of a range of optically active compounds. DFT calculations reveal key noncovalent substrate-ligand interactions that account for the enantioselectivity outcome and the diastereoselective formation of the (Z)-alkenyl chloride.

CuF2/MeOH-Catalyzed N3-Selective Chan-Lam Coupling of Hydantoins: Method and Mechanistic Insight.

An efficient and practical N-arylation of hydantoins with substituted aryl/heteroaryl boronic acids has been established, assisted by CuF2/MeOH under the base and ligand-free conditions at room temperature and open air. The protocol is general, and various N-arylated hydantoins have been prepared in excellent yields with exclusive regioselectivity. The CuF2/MeOH combination was explored further to furnish selective N3-arylation of 5-fluorouracil nucleosides. The efficiency of the protocol was also demonstrated with the gram-scale synthesis of the marketed drug, Nilutamide. A mechanistic study based on density functional theory calculations revealed that both hydantoin and MeOH are crucial for the generation of catalytically active copper species in the reaction process, in addition to their role as a reactant and solvent, respectively. The proposed reaction mechanism indicated that selective N3-arylation of hydantoin is favorable in MeOH, which helps initiate the catalytic cycle by forming a square-planner Cu(II) complex where strong hydrogen-bond interactions are observed. This study is expected to improve the understanding of Cu(II)-catalyzed oxidative N-arylation reactions and for the de novo design and development of Cu-catalyzed coupling reactions.

Effect of Ce-BTC precursor morphology on CuO/CeO2 catalysts for CO preferential oxidation in H2-rich gas

In this paper, the precursors of the coordination polymer Ce(1,3,5-BTC)(H2O)6 with different morphologies have been successfully prepared via a facile and rapid method, and then the CuO/CeO2 catalysts were obtained by impregnation method to support copper species. The catalysts were characterized by scanning electron microscopy, scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis, ultraviolet Raman spectrscopy, N2 adsorption-desorption, H2 programmed temperature reduction and X-ray photoelectron spectroscopy, respectively. The results showed that U–CuCeO catalyst has stronger CuO dispersion and higher oxygen vacancy concentration on the surface. The high specific surface area of U–CuCeO catalyst facilitates the highly dispersed CuO species and enhances the interaction between copper and cerium, and improves the catalytic performance compared with the other catalysts. For U–CuCeO catalyst, the CO conversion reached 100% at 120 °C. It also exihibited the broadest complete reaction temperature window.

Diminishing the catalyst concentration in the Cu(0)‐RDRP and ATRP synthesis of well‐defined low‐molecular weight poly(glycidyl methacrylate)

AbstractLow‐molecular weight (MW) solvent‐borne functional (meth)acrylic polymers find an important use in coating resins. However, when preparing such polymers through copper‐mediated reversible‐deactivation radical polymerization (RDRP), contamination with colored copper species and the use of expensive ligands represent significant obstacles from the industrial application viewpoint. Here, we investigated the possibilities of diminishing the catalyst levels in metallic coper‐mediated RDRP (Cu(0)‐RDRP) and atom transfer radical polymerization (ATRP) of a widely used functional monomer, glycidyl methacrylate (GMA), targeting a low MW of approximately 3000. Both Cu wire‐ and powder‐catalyzed Cu(0)‐RDRP provided well‐defined, low‐MW poly(GMA) at quantitative conversions when using an inexpensive PMDETA ligand in DMSO. However, only with Cu powder, the contamination of the final polymerization mixture with Cu species could be efficiently diminished to ≤66 ppm while maintaining the polymerization control. Additionally, the in situ block copolymerization was successfully demonstrated, furnishing a poly(GMA)‐b‐poly(MMA) mixture containing only 39 ppm of Cu in a process facilitated by the intrinsic reductive properties of the GMA's epoxide groups. Significantly, the targeted low‐MW poly(GMA) could also be synthesized by low‐catalyst‐concentration ATRP (CuBr/PMDETA system), obtaining well‐defined polymers with quantitative conversions at ca 50 ppm of Cu in the final mixture, both at r.t. and 50 °C.

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO2 Revealed by In Situ X‐Ray Spectroscopy

AbstractAdvanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation.

Multiple interface coupling in ultrathin Mn-based composites for superior catalytic oxidation: Implications of interface coupling on structural defects

Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. The modulation of the interfacial coupling effect of manganese oxides by chemical means is considered a critical and effective way to improve the catalytic performance. Herein, a novel one-step synthetic strategy of highly-efficient ultrathin manganese-based catalysts is proposed through optimal regulation of metal/manganese oxide multi-interfacial coupling. Carbon monoxide (CO) and propane (C3H8) oxidation are employed as probe reactions to investigate the structure-catalytic mechanism - catalytic performance relationship. The ultrathin manganese (Mn)-based catalyst exhibits superior low-temperature catalytic activity with a 90% conversion of CO/C3H8 realized at 106℃ and 350℃. Subsequently, the effect of “interfacial effect” on the intrinsic properties of manganese oxides is revealed. The ultrathin appearance of two–dimensional (2D) manganese dioxide (MnO2) nanosheets changes the binding force in the vertical direction, thus resulting in an increase in the average manganese-oxygen (Mn-O) bond length and exposing more surface defects. Besides, the introduction of Copper (Cu) species into the catalyst further weakens the Mn-O bond and promotes the generation of oxygen vacancies, which subsequently enhances the oxygen migration rate. This study provides new insights into the optimal design of transition metal oxide interfacial assemblies for efficient catalytic reactions.

Metal-Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical-Mediated Reactions.

Visible-light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine-ligated copper(I) complexes, we describe herein an effective metal-organic framework (MOF)-supported copper(I) photocatalyst for multiple iminyl radical-mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post-synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF-based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition-metal photoredox catalysis.

Metal‐Organic Framework Supported Copper Photoredox Catalysts for Iminyl Radical‐Mediated Reactions

AbstractVisible‐light copper photocatalysis has recently emerged as a viable technology for building sustainable synthetic processes. To broaden the applications of phosphine‐ligated copper(I) complexes, we describe herein an effective metal‐organic framework (MOF)‐supported copper(I) photocatalyst for multiple iminyl radical‐mediated reactions. Due to site isolation, the heterogenized copper photosensitizer has a significantly higher catalytic activity than its homogeneous counterpart. Using a hydroxamic acid linker to immobilize copper species on MOF supports affords the heterogeneous catalysts with high recyclability. The post‐synthetic modification sequence on MOF surfaces allows for the preparation of previously unavailable monomeric copper species. Our findings highlight the potential of using MOF‐based heterogeneous catalytic systems to address fundamental challenges in the development of synthetic methodologies and mechanistic investigations of transition‐metal photoredox catalysis.

Mechanistic insights into the cobalt promotion on low-temperature NH3-SCR reactivity of Cu/SSZ-13

The ever-increasing demand for nitrogen oxides (NOx) emission control from diesel engines during cold start period has provided a strong impetus to improve the low-temperature NOx removal efficiency of Cu/SSZ-13 catalyst. In this work, a series of bimetallic catalysts CuCo/SSZ-13 with varying cobalt contents were prepared, and attained the significant performance enhancement in NH3 selective catalytic reduction (NH3-SCR) reaction. The promotion mechanism of these catalysts at low temperatures (< 200 °C) was proposed: (1) The introduced Co(II) ions could tune the distributions of copper species and acid sites, resulting in a higher ratio of ZCuOH/Z2Cu (Z represents a negatively charged site on zeolite framework) and much more Lewis acid sites compared with original Cu/SSZ-13. (2) The fast reaction of reactive bridging nitrates with NH3 adsorbed on Lewis acid sites via Langmuir-Hinshelwood (L-H) mechanism decreased the activation energy. However, the addition of high cobalt content facilitated the formation of inactive CuOx species, which was not conducive to maintaining high-temperature (> 500 °C) activity.

Selenium homeostasis in human brain cells: Effects of copper (II) and Se species

BackgroundBoth essential trace elements selenium (Se) and copper (Cu) play an important role in maintaining brain function. Homeostasis of Cu, which is tightly regulated under physiological conditions, seems to be disturbed in Alzheimer´s (AD) and Parkinson´s disease (PD) patients. Excess Cu promotes the formation of oxidative stress, which is thought to be a major cause for development and progression of neurological diseases (NDs). Most selenoproteins exhibit antioxidative properties and may counteract oxidative stress. However, expression of selenoproteins is altered under conditions of Se deficiency. Serum Se levels are decreased in AD and PD patients suggesting Se as an important factor in the development and progression of NDs. The aim of this study was to elucidate the interactions between Cu and Se in human brain cells particularly with respect to Se homeostasis. MethodsFirstly, modulation of Se status by selenite or SeMet were assessed in human astrocytes and human differentiated neurons. Therefore, cellular total Se content, intra- and extracellular selenoprotein P (SELENOP) content, and glutathione peroxidase (GPX) activity were quantified. Secondly, to investigate the impact of Cu on these markers, cells were exposed to copper(II)sulphate (CuSO4) for 48 h. In addition, putative protective effects of Se on Cu-induced toxicity, as measured by cell viability, DNA damage, and neurodegeneration were investigated. ResultsModulation of cellular Se status was strongly dependent on Se species. In detail, SeMet increased total cellular Se and SELENOP content, whereas selenite led to increased GPX activity and SELENOP excretion. Cu treatment resulted in 133-fold higher cellular Cu concentration with a concomitant decrease in Se content. Additionally, SELENOP excretion was suppressed in both cell lines, while GPX activity was diminished only in astrocytes. These effects of Cu could be partially prevented by the addition of Se depending on the cell line and Se species used. While Cu-induced oxidative DNA damage could not be prevented by addition of Se regardless of chemical species, SeMet protected against neurite network degeneration triggered by Cu. ConclusionCu appears to negatively affect Se status in astrocytes and neurons. Especially with regard to an altered homeostasis of those trace elements during aging, this interaction is of high physiological relevance. Increasing Cu concentrations associated with decreased selenoprotein expression or functionality might be a promoting factor for the development of NDs.

Peak-fitting of Cu 2p photoemission spectra in Cu0, Cu1+, and Cu2+ oxides: A method for discriminating Cu0 from Cu1+

The photoemission spectra of Cu 2p are one of the most studied. Its analysis is especially challenging because, among others, the peaks for Cu0 and Cu1+ overlap, and Cu1+ and Cu2+ coexist under many conditions. The chemical state determination of metallic copper and the initial oxidation mechanism of copper require state-of-the-art peak fitting analysis and background modeling. This work presents a detailed and quantitative analysis of the Cu 2p photoemission spectra for a metallic ultra-thin film and the initial oxidation stages. Additionally, annealed films at 200 °C for up to 5 min were analyzed to assess the full oxidation of the copper oxides and assert the validity of the proposed peak-fitting procedures. For the initial oxidation, it was possible to accurately identify Cu1+ and Cu2+ states and, alongside, quantify the corresponding O 1s species, resulting in compositions close to stoichiometric values. Using the active background, it was possible to achieve close reproduction of all the photoemission spectra; three coexisting copper species were resolved during the fitting procedure. An accurate peak-fitting analysis allowed for quantifying the relative proportion of Cu1+ to Cu0 states despite their strong overlap.

Enhanced activation of H2O2 by bimetallic Cu2SnS3: A new insight for Cu (II)/Cu (I) redox cycle promotion

HypothesisDespite that the development of Cu2SnS3 (CTS) catalyst has attracted increasing interests, few study has reported to investigate its heterogeneous catalytic degradation of organic pollutants in a Fenton-like process. Furthermore, the influence of Sn components towards Cu (II)/Cu (I) redox cycling in CTS catalytic systems remains a fascinating research. ExperimentsIn this work, a series of CTS catalysts with controlled crystalline phases were prepared via a microwave-assisted pathway and applied in the H2O2 activation for phenol degradation. The efficiency of phenol degradation in CTS-1/H2O2 system (CTS-1: the molar ratio of Sn (copper acetate) and Cu (tin dichloride) is determined to be Sn:Cu = 1:1) was systematically investigated by controlling various reaction parameters including H2O2 dosage, initial pH and reaction temperature. We discovered that Cu2SnS3 exhibited superior catalytic activity to the contrast monometallic Cu or Sn sulfides and Cu (I) acted as the dominant active sites. The higher Cu (I) proportions conduce to the higher catalytic activities of CTS catalysts. Quenching experiments and electron paramagnetic resonance (EPR) further proved that the activation of H2O2 by CTS catalyst produces reactive oxygen species (ROS) and subsequently leads to degradation of the contaminants. A reasonable mechanism of enhanced H2O2 activation in Fenton-like reaction of CTS/H2O2 system was proposed for phenol degradation by investigating the roles of copper, tin and sulfur species. FindingsThe developed CTS acted as a promising catalyst in Fenton-like oxidation progress for phenol degradation. Importantly, the copper and tin species contribute to a synergetic effect for the promotion of Cu (II)/Cu (I) redox cycle, which thus enhanced the activation of H2O2. Our work may offer new insight on the facilitation of Cu (II)/Cu (I) redox cycle in Cu-based Fenton-like catalytic systems.

Facile synthesis of the atomically dispersed hydrotalcite oxide supported copper catalysts for the selective hydrogenation of 5–hydroxymethylfurfural into 2,5-bis(hydroxymethyl)furan

The selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) using the atomically dispersed supported copper catalyst is investigated. The hydrotalcite oxide supported copper materials (Cu(x)HTO) are facilely prepared by coprecipitating metal precursors in a methanolic solution under a tuned pH. The surface characterization involving PXRD, TEM, H2/N2O-TPR, and XAS reveals unequivocal evidence for the presence of the atomically dispersed copper on HTO surface. XAS specifically indicates the formation of mononuclear copper species, and H2/N2O-TPR strongly supports the copper atoms of Cu(5)HTO are evenly distributed in 99% dispersion. Moreover, the reduced Cu(5)HTO (r-Cu(5)HTO) enables to completely hydrogenate HMF to BHMF under mild conditions, in comparison to the poor reactivity catalyzed by the hydrotalcite oxide supported copper nanoparticles (r-Cu(4)@HTO). The dramatic enhancement of HMF hydrogenation catalyzed by r-Cu(5)HTO can be attributed to the fine distribution of copper atoms which are situated homogeneously over HTO surface as well as chemically reactive for the carbonyl group.

Hydrothermal Aging Alleviates the Phosphorus Poisoning of Cu-SSZ-39 Catalysts for NH3-SCR Reaction.

As a new type of catalyst with the potential for commercial application in NOx removal from diesel engine exhausts, Cu-SSZ-39 catalysts must have excellent resistance to complex and harsh conditions. In this paper, the effects of phosphorus on Cu-SSZ-39 catalysts before and after hydrothermal aging treatment were investigated. Compared with fresh Cu-SSZ-39 catalysts, phosphorus poisoning significantly decreased the low-temperature NH3-SCR catalytic activity. However, such activity loss was alleviated by further hydrothermal aging treatment. To reveal the reason for this interesting result, a variety of characterization techniques including NMR, H2-TPR, X-ray photoelectron spectroscopy, NH3-TPD, and in situ DRIFTS measurements were employed. It was found that Cu-P species produced by phosphorus poisoning decreased the redox ability of active copper species, resulting in the observed low-temperature deactivation. After hydrothermal aging treatment, however, Cu-P species partly decomposed with the formation of active CuOx species and a release of active copper species. As a result, the low-temperature NH3-SCR catalytic activity of Cu-SSZ-39 catalysts was recovered.

One-Step Synthesis of CuxOy/TiO2 Photocatalysts by Laser Pyrolysis for Selective Ethylene Production from Propionic Acid Degradation.

In an effort to produce alkenes in an energy-saving way, this study presents for the first time a photocatalytic process that allows for the obtention of ethylene with high selectivity from propionic acid (PA) degradation. To this end, TiO2 nanoparticles (NPs) modified with copper oxides (CuxOy/TiO2) were synthetised via laser pyrolysis. The atmosphere of synthesis (He or Ar) strongly affects the morphology of photocatalysts and therefore their selectivity towards hydrocarbons (C2H4, C2H6, C4H10) and H2 products. Specifically, CuxOy/TiO2 elaborated under He environment presents highly dispersed copper species and favours the production of C2H6 and H2. On the contrary, CuxOy/TiO2 synthetised under Ar involves copper oxides organised into distinct NPs of ~2 nm diameter and promotes C2H4 as the major hydrocarbon product, with selectivity, i.e., C2H4/CO2 as high as 85% versus 1% obtained with pure TiO2.

Cu-loaded MOF-303 for iodine adsorption: The roles of Cu species and pyrazole ligands

The capture of toxic radioiodine is an increasingly important priority for the safe development of nuclear energy. Copper is a promising alternative for expensive silver to capture iodine. To develop novel copper-based adsorbents and determine the effect of copper species on iodine adsorption, the metal–organic framework with dual-pyrazole ligands (MOF-303) is employed as the scaffold to bind Cu2+ species. Cu0 nanoparticles were formed after the reduction by NaBH4. The obtained Cu2+-MOF-303 and Cu0-MOF-303 show high iodine uptake capacities at 353 K, 747 mg·g−1 and 837 mg·g−1, respectively. They also show high iodine uptake capacities of more than 300 mg·g−1 at a high temperature (423 K), which are better than other Cu-based adsorbents. Besides, the loading of Cu can enhance the iodine selectivity under humid vapor, and iodine adsorption rate in iodine-cyclohexane solutions. The Cu0 on Cu0-MOF-303 can react with iodine directly via the redox mechanism. For Cu2+-MOF-303, the adjacent pyrazole ligands can chelate with Cu2+ ions strongly and transfer charges to trapped iodine to form polyiodide anions, and thus stable CuI species could also be generated. The strategy of anchoring Cu species using MOF-303 provides large channels for iodine diffusion, and highly-dispersed Cu and N sites for iodine capture.

Surface enhanced Raman spectroscopy effect and acicular growth of copper structures on Titania-Silica fibers

The development of copper nanomaterials with dendritic shapes or hedgehog morphologies is of interest due to their optical, electrical, and catalytic properties; and their applications in catalysis and surface enhanced Raman spectroscopy (SERS). Placing the particles on a ceramic matrix gives them support and the properties of both materials is benefit. In this research, a matrix of TiO2SiO2 ceramic fibers doped with copper microstructures was developed, to take advantage of the synergistic effect of both materials, and their ability to amplify signals in Raman spectroscopy was evaluated. Sol-gel and electrospinning techniques were used to obtain the ceramic matrix, and electrodeposition to obtain the copper structures. Characterization by infrared spectroscopy and X-ray diffraction allowed the identification of copper species such as CuO, Cu2O, and Cu(OH)2. In addition, the characterization with scanning electron microscopy allowed to identify morphologies on the fibers of spheres, dendrites, and needles, belonging to copper species. The materials presented SERS amplification factors of 20.23 and 9.51 for TiO2SiO2 fibers and TiO2SiO2Cu doped by 0.75 min respectively, for the 1373 cm−1 band of a 1 × 10−4 M violet crystal solution.

Exploiting Coordination Behavior of 7-Azaindole for Mechanistic Investigation of Chan-Lam Coupling and Application to 7-Azaindole Based Pharmacophores.

Multiple spectroscopic techniques, along with single-crystal X-ray analysis, have been used to reveal the detailed structural and electronic information on reaction intermediates of a new copper(II)-DBU catalytic system for the N-arylation of 7-Azaindole. The reaction mixture of Chan-Lam cross-coupling yields two dimeric copper(II)-7-azaindole complexes, including one attached with DBU, prior to adding arylboronic acid and are confirmed structurally and spectroscopically. A suitable mechanism has been proposed using the dimeric copper(II) complex as a catalyst for the coupling reactions. The role of DBU as a base and also as an auxiliary ligand in the course of the reaction has been established. The transmetalated monomeric aryl-copper(II) species generated from the dimeric unit is oxidized by another equivalent of copper(II) to yield an aryl-copper(III) intermediate for facile N-arylation, which has been authenticated with UV-vis spectroscopy. The regeneration of the copper(II)-catalyst by aerial oxidation of colorless copper(I) species (generated via reductive elimination and disproportionation step) is confirmed by mass and absorption spectroscopy. Detailed DFT and TD-DFT calculations help to rationalize the proposed reaction intermediates and their corresponding electronic transitions. Moreover, the confirmation of copper(I)-7-azaindole intermediate via HRMS reaffirmed the involvement of Cu(II)/Cu(III)/Cu(I) species in the Chan-Lam type of coupling. A medicinally-important 7-azaindole-based SHP2 inhibitor has been synthesized via sequential arylation.

Atomically precise copper dopants in metal clusters boost up stability, fluorescence, and photocatalytic activity

The structurally precise alloy nanoclusters have been emerged as a burgeoning nanomaterial for their unique physical/chemical features. We here report a rod-like nanocluster [Au12Cu13(PPh3)10I7](SbF6)2 (Au12Cu13), which was generated through a transformation of a [Au9(PPh3)8]3+ intermediate in the presence of CuI, unveiled by time-dependent UV-vis spectroscopy, electrospray ionization mass spectrometry as well as single crystal X-ray diffraction. Au12Cu13 is comprised of two pentagonal bipyramids Au6Cu units and a pentagonal prism Cu11 unit, where the copper and gold species are presented in +1 and 0 chemical states. The Cu-dopants significantly improved the stability and fluorescence (quantum yield: ~34%, 34-folds of homo-Au25(PPh3)10Br7). The high stability of Au12Cu13 is attributed to the high binding energy of iodine ligands, Au-Cu synergistic effects and its 16-electon system as an 8-electron superatom dimer. Finally, the robust Au12Cu13 exhibited high catalytic activity (~92% conversion and ~84% methyl formate-selectivity) and good durability in methanol photo-oxidation.