Spherical Nanoclusters Research Articles

Multi-resonance terahertz (THz) generation from magnetized cylindrical and spherical nanoclusters of AlAs and InP nanoparticles

We report a theoretical model for THz generation from the interaction of Gaussian laser beams with semiconductor nanoparticles suspended in argon gas in the presence of a DC magnetic field. Our investigations include two different shapes of nanoparticles [spherical (SNPs) and cylindrical (CNPs)]. The laser fields ionize nanoparticles converting them into plasma, which takes the form of spherical and cylindrical periodic nanoclusters with the electron density profile n=n0+nqeiqz, where q is the wave number of the density ripple and nq is the amplitude of density modulation. In our investigations, nanoparticles of AlAs and InP semiconductors are considered. Resonance condition is obtained when the laser beat frequency matches with the surface plasmon frequency of nanoparticles. We obtain resonances at two different frequencies when we apply a DC magnetic field. The resonance frequencies of THz fields shift with the nanoparticles' shape and orientation. THz field amplitude varies with material properties, spacing, size, and orientation of the nanoparticles. The applied magnetic field enhances the THz field and also helps in controlling the field profile. A THz field ∼0.1GV/cm with ∼2% efficiency is obtained for an optimized set of parameters for CNPs.

Multifunctional aluminum 12-hydroxystearate/lignin polyurethane foam for selective gelation and efficient separation of oil and organic solvents

During frequent transportation, the marine environment is continuously exposed to significant threats from crude oil and organic solvent leakage. Non-covalent self-assembly of organogelator on the adsorbent matrix to fix non-polar solvents is an efficient and sustainable remediation method. This contribution proposes an organogelator-adsorbent composite by blending aluminum 12-hydroxystearate (Al HSA) and expanded graphite (EG) during lignin-based polyurethane foaming. Al HSA molecule synergizes with EG to modulate the shape (hexagonal), oil retention, mechanical property, and hydrophobicity (water contact angle = 151.3°) of the lignin-based polyurethane foam (LPUF) skeleton. Al HSA-LPUF (OTS-LPUF/EAH) superhydrophobic foam exhibits sorption capacity up to 13.2–53.0 g g−1 in various oils and organic solvents. From the microscopic morphology, the Al HSA on the skeleton self-assembles into spherical nanoclusters driven by hydrogen bonding, realizing the capturing of oils and organic solvents. Even after 20 cycles, the foam still has a high oil/water separation capacity and mechanical performance. OTS-LPUF/EAH also shows improved flame retardancy and a 61 % reduction in total smoke release (TSR) compared to pristine LPUF.

Zinc and cadmium thioamidate complexes: rational design of single-source precursors for the AACVD of ZnS.

A series of zinc(II) thioamidate complexes [Zn{SC(iPr)NR}2]n for R = iPr (n = 2) (2), tBu (3) (n = 1), Ph (4) (n = 2) and Cy (5) (n = 2) and one cadmium(II) thioamidate complex [Cd{SC(iPr)NtBu}2]3, (6), were designed and synthesised as single-source precursors for AACVD ZnS and CdS. Solid-state structures of all four zinc(II) compounds revealed distorted tetrahedral or trigonal bipyramidal geometries, with varying tendencies for dimeric association, mediated by {Zn-S} bridging bonds. The thermogravimetric analysis identified the {tBu} derivertive, 3, as the most promising precursor based on its low decomposition onset (118 °C) and clean conversion to ZnS. This was attributed to the greater availability of β-hydrogen atoms promoting the pyrolysis mechanism. The corresponding cadmium thioamide 6 was found to crystallise as a trimetallic molecule which lacked the thermal stability to be considered viable for AACVD. Hence, 3 was used to deposit ZnS thin films by AACVD at 200-300 °C. Powder X-ray diffraction confirmed phase-pure growth of hexagonal wurtzite ZnS, with approximate crystallite sizes of 15-20 nm. Scanning electron microscopy revealed densely packed spherical nanoclusters. The morphology and crystallinity were most consistent for depositions between 250-300 °C. Energy dispersive X-ray spectroscopy indicated slightly sulfur-deficient stoichiometries.

Magnesium-induced evolution of micromorphology on layered double hydroxides for enhanced hybrid supercapacitors

Layered double hydroxide (LDH) materials have demonstrated great potential in the application of supercapacitors by virtue of high theoretical specific capacity, large specific surface area, ease of fabrication and environmentally benign nature. Nevertheless, the issue of worse electrical conductivity and terrible structural stability severely constrains the practical application of LDH materials in the next-generation high-performance energy supply systems. Morphology regulation and element doping have been proved to be two effective pathways to boost the electrochemical performance of materials. In this work, a novel magnesium-doped nickel cobalt layered double hydroxides (NiCoMg-LDH) has been feasibly synthesized on flexible carbon cloth after introducing small amounts of magnesium ions into NiCo-LDH, which contributes to the evolution of micromorphology from pure nanosheets of NiCo-LDH to 3D nanosphere clusters of NiCoMg-LDH. Although magnesium ions make no direct and great capacity contribution unlike nickel ions and cobalt ions possessing mixed valence states, their successful introduction does play a vital role in regulating and controlling the micro-morphology of the as-fabricated NiCoMg-LDH material, and thus the electrochemical characteristics of the NiCoMg-LDH electrode can be successfully improved in an indirect pattern. Compared with NiCo-LDH electrode, NiCoMg-LDH electrode demonstrates much more remarkable electrochemical properties in the respect of specific capacity, rate performance and cycle life. Additionally, the aqueous hybrid supercapacitor (AHSC) NiCoMg-LDH//AC demonstrates a high gravimetric specific energy of 29.3 Wh kg−1 at 750 W kg−1 as well as a satisfactory cyclic lifespan of enduring 5000 CV scans without capacity decay. The facile fabrication and remarkable electrical performance enable this AHSC device to be an appropriate candidate with enormous potential for practical applications.

Metallic (Cum)n+ quantum nanoclusters through the lithium metaphosphate network: Efficient energy transfer to Mn2+ ions for white LED

Metallic (Cum)n+ nanoclusters are superior to their (Aum)n+ and (Agm)n+ counterparts in the aspect of being relatively cheap for wide industrial demands. However, further improvements are still needed, especially in terms of the generation of (Cum)n+ nanoclusters. Herein, (Cum)n+ has been successfully generated with Mn2+ ions into 2.5MnO·47.5Li2O·50P2O5 (MnP), 2.5CuO·47.5Li2O·50P2O5 (CuP) and 2.5MnO·2.5CuO·45Li2O·50P2O5 (CuMnP) matrices. This generation has been demonstrated by XRD, XPS, TEM, SEM, AFM, UV–Vis and PL analyses. MnP displays an amorphous nature with red light emission under an excitation wavelength of 409 nm due to the 4T1(G)→6A1(S) transition of Mn2+ ions. CuP and CuMnP exhibit the formation of spherical nanoclusters with a size less than 10 nm. These nanoclusters are attributed to (Cum)n+, which exhibit tunable emission from blue to white to red light as the excitation wavelength changes from 270 to 360 nm. When MnP, CuP and CuMnP are subjected to 380 °C for 4, 1 and 1 h, respectively, the LiPO3 crystalline phase has evolved. This is associated with the reduction of (Cum)n+ to plasmonic (Cu°)n nanoparticles, and therefore crystallization-induced photoluminescence weakening. This demonstrates that the lithium metaphosphate glassy matrix provides an efficient emission as compared to the corresponding LiPO3 crystalline phase. Overall, in the CuMnP matrix, there is an efficient energy transfer from (Cum)n+ to Mn2+ as the 1Eg excited level of (Cum)n+ is higher than the 4A1/4E energy levels of Mn2+ ions. This synergistic Mn2+/(Cum)n+ combination has resulted in the generation of a rare earth-free platform promised for white LED applications.

Symmetry and Electronic Properties of Metallic Nanoclusters

Spherical nanoclusters with countable member atoms and delocalized valence orbitals are superatoms with properties analogous to those of simple atoms. This is reflected, in particular, in their optical spectra and magnetic properties, in a similar sense to transition metal ions and complexes. Clusters can be of low-spin or high-spin with considerable contributions to magnetism by the large cluster orbital magnetic moment. Due to the large radius of the clusters, they can be diamagnetic with an unusually high diamagnetic susceptibility. Gold and platinum, which in the bulk are non-magnetic, show pronounced superparamagnetism associated with their high-spin nature, and the magnetic moment can be trapped in symmetry-breaking environments so that hysteresis pertains far beyond room temperature. A significant deviation from hydrogen-like orbitals results from the shape of the confining potential, which has the effect that the orbital quantum number ℓ is not limited to values less than the principal quantum number n.

Numerical simulation of photonic nanojet produced by globular cluster of dielectric nanospheres

Near-field focusing of an optical wave by nanoparticle clusters aggregated into a globule (a "metaparticle") is considered for different nanoparticle concentration, size and optical properties. Our numerical simulations show that the self-assembly of spherical nanoparticles into a globular photonic structure can also produce the focal regions of enhanced optical intensity existing in the spatial form of a photonic nanojet (PNJ). A detailed study of all significant PNJ parameters depending on the cluster topology and optical properties of the nanostructure filling is carried out. We determine the conditions when it is possible conditional substitution the nanoparticle cluster by a homogeneous microsphere with the same geometrical dimensions but with some effective refractive index. Besides, we show that in some cases the globular nanosphere clusters is able to produce a PNJ with improved parameters, particularly, with higher spatial localization and increased intensity.

Spherical lanthanide nanoclusters toward white-light emission and cell membrane imaging

Spherical lanthanide nanoclusters toward white-light emission and cell membrane imaging

Real-space solution to the electronic structure problem for nearly a million electrons.

We report a Kohn-Sham density functional theory calculation of a system with more than 200 000 atoms and 800 000 electrons using a real-space high-order finite-difference method to investigate the electronic structure of large spherical silicon nanoclusters. Our system of choice was a 20nm large spherical nanocluster with 202 617 silicon atoms and 13 836 hydrogen atoms used to passivate the dangling surface bonds. To speed up the convergence of the eigenspace, we utilized Chebyshev-filtered subspace iteration, and for sparse matrix-vector multiplications, we used blockwise Hilbert space-filling curves, implemented in the PARSEC code. For this calculation, we also replaced our orthonormalization + Rayleigh-Ritz step with a generalized eigenvalue problem step. We utilized all of the 8192 nodes (458 752 processors) on the Frontera machine at the Texas Advanced Computing Center. We achieved two Chebyshev-filtered subspace iterations, yielding a good approximation of the electronic density of states. Our work pushes the limits on the capabilities of the current electronic structure solvers to nearly 106 electrons and demonstrates the potential of the real-space approach to efficiently parallelize large calculations on modern high-performance computing platforms.

Solving the electronic structure problem for over 100 000 atoms in real space

Using a real-space high-order finite-difference approach, we investigate the electronic structure of large spherical silicon nanoclusters. Within Kohn-Sham density functional theory and using pseudopotentials, we report the self-consistent field convergence of a system with over 100 000 atoms: a ${\mathrm{Si}}_{107,641}{\mathrm{H}}_{9,084}$ nanocluster with a diameter of 16 nm. Our approach uses Chebyshev-filtered subspace iteration to speed up the convergence of the eigenspace, and blockwise Hilbert space-filling curves to speed up sparse matrix-vector multiplications, all of which are implemented in the parsec code. For the largest system, we utilized 2048 nodes (114 688 cores) on the Frontera machine in the Texas Advanced Computing Center. Our quantitative analysis of the electronic structure shows how it gradually approaches its bulk counterpart as a function of nanocluster size. The band gap is enlarged due to quantum confinement in nanoclusters, but decreases as the system size increases, as expected. Our work serves as a proof of concept for the capacity of the real-space approach in efficiently parallelizing very large calculations using high-performance computer platforms, which can straightforwardly be replicated in other systems with more than ${10}^{5}$ atoms.

Molecular dynamics simulation and experimental investigation of mechanical properties of calcium carbonate and graphene reinforced polylactic acid nanocomposites.

The use of Molecular Dynamics (MD) simulations to examine the mechanical characteristics of polymer compositesreinforced with calcium carbonate (CaCO3) and graphene (GR) is represented in this work. The effects of CaCO3 andGR nanoadditives in polylactic acid (PLA) matrix in different concentrations were evaluated using the results of MDsimulations. Experimental analyses have been conducted to validate the results of MD based on the mechanicalproperties of fabricated nanocomposites, including modulus of elasticity, shear modulus, and Poisson's ratio. Themodeling, computation, and analysis of several simulations on the improved mechanical characteristics ofPLA/CaCO3 and PLA/GR nanocomposites are introduced and discussed. The results revealed that the addition ofGR nanoparticles were more effective in enhancing the mechanical properties of PLA components as compared withthat of CaCO3 nanoparticles, as the modulus of elasticity, shear modulus and Poisson's ratio increased byapproximately 21%, 17%, and 16% for addition of 3 wt% GR nanoparticles in the PLA matrix, respectively. The mechanical behavior of PLA/CaCO3 and PLA/GR nanocomposites have been simulated based on the moleculardynamic technique using material studio (MS) that enabled the analyses of synergy between the polymer moleculesand the nanoparticles. Molecular models for a system of nanocomposites were built by embedding the nano-clustersinto an amorphous PLA matrix. Nanoparticles have been modeled as spherical nanoclusters of graphite and calciteunit cells. Molecular models of the pure PLA matrix were also developed for comparison. The relaxed systems of MDsimulations have been carried out to calculate the mechanical properties of nanocomposites containing 1, 3 and 5wt% nanofiller contents. To validate the results of the simulations, the PLA/CaCO3 and PLA/GR nanocompositegranules, containing different weight ratios of the nanofillers in the matrix, have been synthesized by melt-blendingtechnique. These granules have been used to produce tensile test samples by injection molding technique, withdifferent fractions of nanoparticles in the matrix, to study the effects of such nanoadditives on the mechanicalproperties of the PLA nanocomposites.

High-stability spherical lanthanide nanoclusters for magnetic resonance imaging.

High-nuclear lanthanide clusters have shown great potential for the administration of high-dose mononuclear gadolinium chelates in magnetic resonance imaging (MRI). The development of high-nuclear lanthanide clusters with excellent solubility and high stability in water or solution has been challenging and is very important for expanding the performance of MRI. We used N-methylbenzimidazole-2-methanol (HL) and LnCl3·6H2O to synthesize two spherical lanthanide clusters, Ln32 (Ln = Ho, Ho32; and Ln = Gd, Gd32), which are highly stable in solution. The 24 ligands L- are all distributed on the periphery of Ln32 and tightly wrap the cluster core, ensuring that the cluster is stable. Notably, Ho32 can remain highly stable when bombarded with different ion source energies in HRESI-MS or immersed in an aqueous solution of different pH values for 24 h. The possible formation mechanism of Ho32 was proposed to be Ho(III), (L)- and H2O → Ho3(L)3/Ho3(L)4 → Ho4(L)4/Ho4(L)5 → Ho6(L)6/Ho6(L)7 → Ho16(L)19 → Ho28(L)15 → Ho32(L)24/Ho32(L)21/Ho32(L)23. To the best of our knowledge, this is the first study of the assembly mechanism of spherical high-nuclear lanthanide clusters. Spherical cluster Gd32, a form of highly aggregated Gd(III), exhibits a high longitudinal relaxation rate (1 T, r1 = 265.87 mM-1·s-1). More notably, compared with the clinically used commercial material Gd-DTPA, Gd32 has a clearer and higher-contrast T1-weighted MRI effect in mice bearing 4T1 tumors. This is the first time that high-nuclear lanthanide clusters with high water stability have been utilized for MRI. High-nuclear Gd clusters containing highly aggregated Gd(III) at the molecular level have higher imaging contrast than traditional Gd chelates; thus, using large doses of traditional gadolinium contrast agents can be avoided.

Landau theory and self-assembly of spherical nanoclusters and nanoparticles with octahedral symmetry

Spherical nanoclusters and nanoparticles are rising materials whose functional design provides many useful applications ranging from catalysis, molecular sensing, gas storage to drug targeting and delivery. Here, we develop phenomenological crystallization theory of such spherical structures with octahedral symmetries O and O_h. Within the developed theory, we propose a method, which is based on constructing irreducible octahedral density functions and allows to predict the positions of structural units in the spherical nanoobjects. The proposed theory explains the structures of the simplest known metal nanoclusters, some metal-organic polyhedra and membrane protein polyhedral nanoparticles, and also predicts more complex chiral spherical structures and achiral assemblies characterized by the geometry of semiregular polyhedra. A relationship between the constructed irreducible octahedral functions and spherical lattices, obtained by mapping a plane hexagonal order onto a spherical surface through an octahedron net, is discussed as well.

Size- and Shape-Dependent Photoexcitation Electron Transfer in Metal Nanoclusters

There are some unresolved fundamental issues for metal nanoclusters; for instance, the close-packed structure transformation from face-centered cubic (fcc) to hexagonal close-packed (hcp) has not yet been reported, and photoexcitation electron transfer is not well understood. Herein, we realized for the first time the fcc-to-hcp structure transformation and revealed the size- and shape-dependent photoexcitation electron transfer for metal nanoclusters. Specifically, a thermally induced ligand exchange method was developed, and a rod-shaped hcp Au42(SCH2Ph)32 (HSCH2Ph: benzyl mercaptan) with the largest aspect ratio was synthesized from fcc Au28(SPh-tBu)20 (HSPh-tBu: p-tert-butylphenol) and structurally resolved, which shows a sharp absorption at 815 nm and dual emission that is well interpreted by time-dependent density functional theory (TD-DFT) calculations. The structure transformation pathway was proposed, and a novel, rod-shaped hcp Au58(SR)40 with larger aspect ratio was predicted. Interestingly, it is found that the kernel-based middle-to-both ends sp ← sp photoexcitation electron transfer can be extended to other rod-like (one-dimensional) gold nanoclusters, and the major photoexcitation turns to the kernel-based sp ← sp transition from the staple-to-kernel sp ← d transition when the spherical gold nanocluster size is increased to Au42 and the Au(6sp) composition increases with increasing size for structure-similar nanoclusters. These findings deepen our understanding of metal nanocluster photoexcitation electron transfer and provide guidance for future nanocluster property tuning aimed at practical applications.

A sandwich-type electrochemical immunosensor based on spherical nucleic acids-templated Ag nanoclusters for ultrasensitive detection of tumor biomarker

The accurate determination of tumor biomarkers in blood is of vital significance in the diagnosis and therapy of tumor disease. In this research, an innovative sandwich-type electrochemical immunosensor is designed for the ultrasensitive determination of tumor biomarker AFP using spherical nucleic acids-templated silver nanoclusters (AgNCs) sensing platform. For this purpose, on one hand, DNA functionalized gold nanoparticles (AuNPs@DNA) is selected not only as the cross-linker to immobilize the primary antibody (anti-AFP antibody 1, Ab1) to obtain AuNPs@DNA-Ab1, but also as the template for synthesizing AgNCs on AuNPs to form AuNPs@DNA-AgNCs. On the other hand, p-sulfonated calix[4]arene (pSC4) modified Au is chosen to immobilize the secondary antibody (anti-AFP antibody 2, Ab2) through host-guest recognition between Ab2 and pSC4. When AFP is encountered, the immunoreaction signal can be significantly amplified by the electrochemical reduction of AgNCs. Under optimal circumstances, the sandwich-type electrochemical immunosensor exhibits broad limit of linearity from 0.001 to 100 ng mL−1 (R2 = 0.997) and low detection limit of 7.74 fg mL−1 (S/N = 3). The immunosensor possesses excellent repeatability and selectivity, offering a novel method for sensitive clinical diagnosis of tumor markers in human hepatocellular carcinoma.

The Magic and Spherical Metallic Nanoclusters and Their Properties as Nuclei at Phase Transitions, in Particular, at Electrocrystallization

The Magic and Spherical Metallic Nanoclusters and Their Properties as Nuclei at Phase Transitions, in Particular, at Electrocrystallization

Nanomechanical properties of PVDF–ZnO polymer nanocomposite

Poly(vinylidenefluoride)–ZnO (PVDF–ZnO) nanocomposites with mechanically activated ZnO nanoparticle fillers were investigated using thermal and mechanical analysis and AFM and PFM. Differential scanning calorimetry (DSC) investigated the effect of ZnO nanoparticles on the crystallinity of the polymer, under controlled heating and cooling. Atomic force (AFM) microscopy was used to record the surfaces of the samples. Nanocomposite surface roughness shows the presence of the different phases inside of the matrix, where rough samples contain a higher proportion of the β phase. PFM was performed to investigate the piezoresponse of the composites. Nanoidentation showed that the mechanical activation of the filler (ZnO) increases the Young modulus with the activation time. Molecular simulations in periodic systems (PVDF–ZnO spherical nanocluster and nanocylinder composite) were used to investigate the influence of particle size and shape on the Young modulus of different phases of PVDF.

Highly sensitive photoelectrochemical detection of cancer biomarkers based on CdS/Ni-CAT-1 nanorod arrays Z-scheme heterojunction with spherical nucleic acids-templated copper nanoclusters as signal amplification

Ultrasensitive and accurate detection of low-abundance cancer markers is critical for early diagnosis of cancer. To date, developing high-performance photoelectrode and efficient signal amplification strategies remain core challenges for photoelectrochemical bioanalysis. Herein, a CdS/conductive metal-organic frameworks nickel-catecholates nanorod (Ni-CAT-1 NR) arrays Z-scheme heterojunction was developed as a high-performance photoelectrode for split-type photoelectrochemical aptasensing of carcinoembryonic antigen (CEA, as a model cancer marker) with advanced spherical nucleic acids-templated copper nanoclusters (SNAs-Cu NCs) as signal amplification. The Ni-CAT-1 NR arrays not only match with the energy band of CdS, but also act as a direct pathway for electron transfer to the electrode surface, reducing the photogenerated charges recombination rate. In the presence of CEA, aptamer-modified magnetic beads and aptamer-anchored SNAs-Cu NCs reacted with the target to form a sandwich-like structure and plenty of Cu2+ released from SNAs-Cu NCs by acidolysis could react with CdS/Ni-CAT-1 NR arrays to generate trapping site, reducing the photocurrent. Under optimal conditions, the prepared aptasensor showed a wide linear range from 0.01 pg mL−1-1.0 ng mL−1, a low detection limit of 0.003 pg mL−1, and excellent stability and accuracy, demonstrating a promising platform for biomarkers detection.

As (III) removal using superparamagnetic magnetite nanoparticles synthesized using Ulva prolifera − optimization, isotherm, kinetic and equilibrium studies

In this study, magnetite nanoparticles (MNPs) were synthesized using the seaweed – Ulva prolifera, an amply found marine source in the Western coastal regions of India. The surface and other properties of MNPs were characterized by many sophisticated methods. Spherical nanoclusters were observed in the FESEM image and iron and oxygen elements were seen in EDS results. XRD peaks were consistent with magnetite standards and MNPs had good crystallinity. FTIR portrayed the specific signals for MNPs and TGA profile ascertained the thermal stability. Magnetic saturation of 41.84 emu/g with negligible hysteresis loop substantiated the superparamagnetism. XPS pointed out the presence of Fe and O with oxidation states specific for MNPs, and the results were consistent with EDS. BET revealed a high specific surface area (144.98 m2/g) of MNPs with mesopores. The synthesized MNPs were used as nanoadsorbent for the removal of As (III) from aqueous solution. The central composite design was used for optimizing As (III) adsorption on MNPs. The optimum conditions were found out as 97.5% at pH: 9, rotation speed: 150 rpm, time: 90 min, and MNPs dosage: 1.15 g/L. The adsorption process fitted in a better way with the Langmuir isotherm and pseudo-second-order model. The highest adsorption capacity was 12.45 mg/g, which is substantially larger than the documenter reports. The spontaneous and endothermic nature of adsorption were ascertained from thermodynamic studies. The results suggested that the synthesized MNPs using the extract of U. prolifera could be alternative nanoadsorbents for eliminating toxic heavy metals from waste streams.

The reaction mechanism of highly dispersed Cu atoms and ultrafine MnOx nanoclusters co-modified ZSM-5 based on in-situ heteronuclear substitution for catalytic oxidation C6H14

A series of Mn/Cu cosubstituted ZSM-5 (Zeolite Socony Mobil–5) with different Mn/Cu molar ratios were synthesized by a one-step heteronuclear substitution hydrothermal method. Singly substituted Mn- and Cu-ZSM-5 compounds were also prepared. The catalytic oxidation performance of hexane and the catalyst surface physicochemical properties over each catalyst were investigated to determine the reaction activity, the main influencing factors and the mechanism for hexane oxidation. Part of the framework Mn of ZSM-5 was substituted by Cu2+ during Mn/Cu cosubstitution, facilitating the generation of isolated and/or framework Cu2+ and extraframework ultrafine hollow spherical MnOx nanoclusters, and increasing the low-temperature reducibility and the amount and transfer capacity of superficial lattice oxygen. Mn-Cu-HZ(1:1) with an appropriate Mn/Cu cosubstitution ratio exhibited the best catalytic oxidation performance, mainly because it has the most superficial lattice oxygens, a relatively high transfer capacity, the highest low-temperature reducibility and suitable acidity. Synergetic catalysis could occur between isolated and/or framework Cu2+ and ultrafine MnOx nanoclusters via a Mars-Van Krevelen (MvK) mechanism. A reaction route for hexane oxidation over Mn-Cu-HZ(1:1) was proposed based on the in situ DRIFTS and GC–MS results. This work provides new insights into the design of VOC degradation catalysts.