Small Nanoclusters Research Articles

Stability Changes in Iridium Nanoclusters via Monoxide Adsorption: A DFT Study within the van der Waals Corrections.

Small iridium nanoclusters are prominent subnanometric systems for catalysis-related applications, mainly because of a large surface-to-volume ratio, noncoalescence feature, and tunable properties, which are completely influenced by the number of atoms, geometry, and molecular interaction with the chemical environment. Herein, we investigate the interaction between Irn nanoclusters (n = 2-7) and polluting molecules, CO, NO, and SO, using van der Waals D3 corrected density functional theory calculations. Starting from a representative structural set, we determine the growth pattern of the lowest energy unprotected Irn nanoclusters, which is based on open structural motifs, and from the adsorption of a XO (X = C, N, and S) molecule, the preferred high-symmetric adsorption sites were determined, dominated by the onefold top site. For protected systems, 4XO/Ir4 and 6XO/Ir6, we found a reduction in the total magnetic moment, while the equilibrium bonds of the nanoclusters expanded (contracted) due to mCO and mNO (mSO) adsorption, with exceptions for systems with large structural distortions (4SO/Ir4 and 6NO/Ir6). Meanwhile, the C-O and N-O (S-O) bond strength decreases (increases) following an increase (decrease) in the C-O and N-O (S-O) distances upon adsorption. We show, through energetic analysis, that for the different chemical environments, relative stability changes occur from the most stable unprotected nanoclusters, planar square (Ir4), and prism (Ir6) to higher energy isomers. The change in the stability order between the two competing protected systems is feasible if the balance between the interaction energy (additive term) and distortion energies (nonadditive terms) compensates for the relative total energies of the unprotected configurations. For all systems, the interaction energy is the main reason responsible for stability alterations, except for 4SO/Ir4, where the main contribution is from a small penalty due to Ir4 distortions upon adsorption, and for 4NO/Ir4, where the energetic effects from the adsorption do not overcome the difference between the binding energies of the unprotected nanoclusters. Finally, from energy decomposition and Hirshfeld charge analysis, we find a predominant covalent nature of the physical contributions in mOX···Irn interactions with a cationic core (Irn) and an anionic shell (XO coverage).

Lanthanide Ions Sensitization by Small Noble Metal Nanoclusters

Rare-earth ions sensitization is, nowadays, a relevant topic in modern technologies. Noble metal nanoclusters can effectively sensitize lanthanide photoluminecence (PL) via excitation energy transfer (EET). Recent experimental works reported how this process strongly depends on the nanoclusters size and composition, however, a comprehensive understanding of this phenomenon is still lacking. Inspired by the current paradigm on the lanthanide–antenna complexes, where light is absorbed by the organic ligand, which then converts to a triplet and transfers the excitation to the lanthanide, we propose it also applies to sensitization by metal clusters. To prove this, we studied the optoelectronic features of several MN nanoclusters (M = Au, Ag, Au/Ag mix; N = 12, 20, and 58) at the Time Dependent Density Functional Theory (TDDFT) level, including, via simplified models, the silica matrix and its possible defects, and make considerations on the role these features can have on the EET toward Er3+ ions. Our analysis suggests that PL enhancement is generally more effective when N = 12 and M = Ag or Au/Ag mix, while the worst cases are obtained when M = Au and N = 58. These findings are coherent with prior experimental data and with novel measures that are here presented for the first time. Notably, we recover that the matrix defects can actively take part in the EET and, in some cases, could be (counterintuitively) beneficial for the process efficiency. Globally, this theoretical framework gives a comprensive rationale that can guide the design of new effective rare-earth ion sensitizers based on metal clusters.

Effect of “Magic” fcc Numbers on the Stability of the Structure of Small Silver Nanoclusters

Effect of “Magic” fcc Numbers on the Stability of the Structure of Small Silver Nanoclusters

Activatable NIR-II Fluorescent Probes Applied in Biomedicine: Progress and Perspectives.

With the advantage of inherent responsiveness that can change the spectroscopic signals from "off" to "on" state in responding to targets (e. g. biological analytes/microenvironmental factors), activatable fluorescent probes have attracted extensive attention and made significant progress in the field of bioimaging and biosensing. Due to the high depth of tissue penetration, minimal tissue damage and negligible background signal at longer wavelengths, the development of second near-infrared window (NIR-II) fluorescent materials provides a new opportunity to develop activable fluorescent probes. Here, we summarized properties, advantages and disadvantages of mainly NIR-II fluorophores (such as rare earth-doped nanoparticles, quantum dots, single-walled carbon nanotubes, small molecule dyes, conjugated polymers and gold nanoclusters), then overviewed current role and development of activatable NIR-II fluorescent probes (AFPs) for biomedical applications including biosensing, bioimaging and therapeutic. The potential challenges and perspectives of AFPs in deep-tissue imaging and clinical application are also discussed.

Unraveling the Causes of the Instability of Aun(SR)x Nanoclusters on Au(111)

Properties of small metal nanoclusters rely on the exact arrangement of a few atoms. Minor structural changes can rapidly destabilize them, leading to disintegration. Here, we evaluate the energeti...

Melting and thermodynamic properties of nanoscale binary chloride salt as high-temperature energy storage material

Phase change heat transfer in nanoporous shape-stabilised phase change materials (ss-PCMs) is of great importance for the efficient utilization of novel energy storage materials. However, the lack of thermodynamic properties hinders the study on phase change heat transfer. In this paper, we selected the binary chloride salts (NaCl–KCl), the promising high-temperature energy storage materials for concentrating solar power, and computed their melting point using the molecular dynamics method. This study not only provides the most fundamental thermal information for the study on phase change heat transfer but reveals the mechanism of the size dependence of melting point from the aspect of the atoms. It is found that the ions in small nanoclusters vibrate more intensely and the crystal structure is easier to be destroyed, leading to lower melting point. The ion self-diffusion coefficient is also computed and analysed from the local microstructure; and it is found that the coefficient is not affected remarkably by the component and the size of nanoclusters.

Designing self-assembling kinetics with differentiable statistical physics models

The inverse problem of designing component interactions to target emergent structure is fundamental to numerous applications in biotechnology, materials science, and statistical physics. Equally important is the inverse problem of designing emergent kinetics, but this has received considerably less attention. Using recent advances in automatic differentiation, we show how kinetic pathways can be precisely designed by directly differentiating through statistical physics models, namely free energy calculations and molecular dynamics simulations. We consider two systems that are crucial to our understanding of structural self-assembly: bulk crystallization and small nanoclusters. In each case, we are able to assemble precise dynamical features. Using gradient information, we manipulate interactions among constituent particles to tune the rate at which these systems yield specific structures of interest. Moreover, we use this approach to learn nontrivial features about the high-dimensional design space, allowing us to accurately predict when multiple kinetic features can be simultaneously and independently controlled. These results provide a concrete and generalizable foundation for studying nonstructural self-assembly, including kinetic properties as well as other complex emergent properties, in a vast array of systems.

Size and shape effects on the stability, electronic structure, and Raman spectroscopy of (SrO)n nanoclusters

AbstractStructural, electronic, and Raman scattering properties of strontium oxide nanoclusters are assessed through density functional theory. Binding energy and second‐order energy calculations clearly show the role played by the geometry on the relative stability of the (SrO)n clusters, revealing that by deviating from cuboid shape these systems tend to become less stable and therefore more reactive, leading to a higher electron affinity and lower ionization potential. Size and shape effects observed in Raman scattering indicate that it might be feasible to discriminate between one and two‐dimensional grown clusters. Additionally, signatures of clusters possessing rings in the structure are also identified in Raman spectra. The results thus suggest that Raman spectroscopy could be an interesting alternative experimental technique to better characterize small nanoclusters.

Quantitative evaluation of spinodal decomposition in thermally aged binary Fe-35 at.% Cr alloys by correlative atom probe tomography and small angle neutron scattering analyses

In this work, spinodal decomposition (SD) in Fe-35 at.% Cr alloy is quantified by correlatively combining two complimentary techniques namely, Atom Probe Tomography (APT) and Small Angle Neutron Scattering (SANS). In order to overcome the uncertainty often encountered in quantification of the characteristic SD parameters (wavelength λSD, amplitude A and volume fraction of Cr-rich α/-phase Φ), we adopt the following: (i) utilize the unique specific attribute of a technique suitable for evaluating any particular SD parameter; (ii) incorporate such reliably extracted parameter as input for evaluating other parameters wherever applicable. This novel correlative approach builds on each other's strength and provides improved accuracy. λSD is determined independently from APT and SANS analyses. For evaluation of A and Φ, APT analysis utilizes the value of λSD determined from SANS, whereas the phase compositions evaluated by APT are utilized in SANS analysis. With progressive phase separation, α/α/ compositional difference increases continually (from 19.8% after 10 h to 48.2% after 500 h) along with concomitant contraction of the interface (from 1.92 nm to 1.55 nm), underscoring the distinctive characteristics of SD process. Signature of rarely observed early stage of phase separation in the form of a dense population (9.78 × 1024/m3) of extremely small (0.67 nm radius) Cr-rich nanoclusters is registered after aging only for 1 h. In addition, temporal evolution of λSD clearly distinguishes early stage of SD (time exponent of 0.15) from the coarsening stage (time exponent of 0.29, 120 h onwards).

Interplay between Chemical Transformations and Atomic Structure in Nanocrystals and Nanoclusters.

ConspectusChemically induced transformations are postsynthetic processing reactions applied to first generation (as-synthesized) nanomaterials to modify property-defining factors such as atomic structure, chemical composition, surface chemistry, and/or morphology. Compared with conditions for direct synthesis of colloidal nanocrystals, postsynthetic chemical transformations can be conducted in relatively mild conditions with a more controllable process, which makes them suitable for the precise manipulation of nanomaterials and for trapping metastable phases that are typically inaccessible from the conventional synthetic routes. Each of the chemically induced transformations methods can result in substantial restructuring of the atomic structure, but their transformation pathways can be very different. And the converse is also true: the atomic structure of the parent material plays a large role in the pathway toward and the resulting chemically transformed product. Additionally, the characteristic length of the parent material greatly affects the structure, which affects the outcome of the reaction.In this Account, we show how the atomic structure and nanoscale size directs the product formation into materials that are inaccessible from analogous chemically transformations in bulk materials. Through examples from the three chemical transformation processes (cation/anion exchange, redox reactions, and ligand exchange and ligand etching), the effect of the atomic structure on chemical transformations is made apparent, and vice versa. For cation exchange, an anisotropic atomic lattice results in a unidirectional exchange boundary. And because the interface can extend through the full crystal, a substantial strain field can form, influencing the phase of the material. In the redox reaction that leads to the nanoscale Kirkendall effect, the atomic structure is the key to inverting the diffusion rates in a diffusion couple to form the hollow cores. And for ligand etching, if one of the materials in a heterostructure has a defected and\or defect-tolerant atomic structure, it can be preferentially etched and its atomic structure can undergo phase transformations while the other composition remains intact. For length scales, we show how the chemically induced transformations greatly differ between bulk, nanocrystal, and nanocluster characteristic sizes. For instance, the structural transformation on relatively large nanocrystals (2-100 nm) can be a continuous process when the activation volume is smaller than the nanocrystal, while for smaller nanoclusters (<2 nm) the transformation kinetics could be swift resulting in only discrete thermodynamic states. Comparing the two nanosystems (nanocrystals to small nanoclusters), we address how their atomic structural differences can direct the divergent transformation phenomena and the corresponding mechanisms. Understanding the nanoscale mechanisms of chemically induced transformations and how they differ from bulk processes is key to unlocking new science and for implementing this processing for functional materials.

Size-controlled nanocrystals reveal spatial dependence and severity of nanoparticle coalescence and Ostwald ripening in sintering phenomena.

A major aim in the synthesis of nanomaterials is the development of stable materials for high-temperature applications. Although the thermal coarsening of small and active nanocrystals into less active aggregates is universal in material deactivation, the atomic mechanisms governing nanocrystal growth remain elusive. By utilizing colloidally synthesized Pd/SiO2 powder nanocomposites with controlled nanocrystal sizes and spatial arrangements, we unravel the competing contributions of particle coalescence and atomic ripening processes in nanocrystal growth. Through the study of size-controlled nanocrystals, we can uniquely identify the presence of either nanocrystal dimers or smaller nanoclusters, which indicate the relative contributions of these two processes. By controlling and tracking the nanocrystal density, we demonstrate the spatial dependence of nanocrystal coalescence and the spatial independence of Ostwald (atomic) ripening. Overall, we prove that the most significant loss of the nanocrystal surface area is due to high-temperature atomic ripening. This observation is in quantitative agreement with changes in the nanocrystal density produced by simulations of atomic exchange. Using well-defined colloidal materials, we extend our analysis to explain the unusual high-temperature stability of Au/SiO2 materials up to 800 °C.

Copper nanoclusters: designed synthesis, structural diversity, and multiplatform applications

Atomically precise metal nanoclusters (MNCs) have gained tremendous research interest in recent years due to their extraordinary properties. The molecular-like properties that originate from the quantized electronic states provide novel opportunities for the construction of unique nanomaterials possessing rich molecular-like absorption, luminescence, and magnetic properties. The field of monolayer-protected metal nanoclusters, especially copper, with well-defined molecular structures and compositions, is relatively new, about two to three decades old. Nevertheless, the massive progress in the field illustrates the importance of such nanoobjects as promising materials for various applications. In this respect, nanocluster-based catalysts have become very popular, showing high efficiencies and activities for the catalytic conversion of chemical compounds. Biomedical applications of clusters are an active research field aimed at finding better fluorescent contrast agents, therapeutic pharmaceuticals for the treatment and prevention of diseases, the early diagnosis of cancers and other potent diseases, especially at early stages. A huge library of structures and the compositions of copper nanoclusters (CuNCs) with atomic precisions have already been discovered during last few decades; however, there are many concerns to be addressed and questions to be answered. Hopefully, in future, with the combined efforts of material scientists, inorganic chemists, and computational scientists, a thorough understanding of the unique molecular-like properties of metal nanoclusters will be achieved. This, on the other hand, will allow the interdisciplinary researchers to design novel catalysts, biosensors, or therapeutic agents using highly structured, atomically precise, and stable CuNCs. Thus, we hope this review will guide the reader through the field of CuNCs, while discussing the main achievements and improvements, along with challenges and drawbacks that one needs to face and overcome.

Mixed‐Metal MOF‐74 Templated Catalysts for Efficient Carbon Dioxide Capture and Methanation

AbstractThe vast chemical and structural tunability of metal–organic frameworks (MOFs) are beginning to be harnessed as functional supports for catalytic nanoparticles spanning a range of applications. However, a lack of straightforward methods for producing nanoparticle‐encapsulated MOFs as efficient heterogeneous catalysts limits their usage. Herein, a mixed‐metal MOF, NiMg‐MOF‐74, is utilized as a template to disperse small Ni nanoclusters throughout the parent MOF. By exploiting the difference in NiO and MgO coordination bond strength, Ni2+ is selectively reduced to form highly dispersed Ni nanoclusters constrained by the parent MOF pore diameter, while Mg2+ remains coordinated in the framework. By varying the ratio of Ni to Mg in the parent MOF, accessible surface area and crystallinity can be tuned upon thermal treatment, influencing CO2 adsorption capacity and hydrogenation selectivity. The resulting Ni nanoclusters prove to be an active catalyst for CO2 methanation and are examined using extended X‐ray absorption fine structure and X‐ray photoelectron spectroscopy. By preserving a segment of the Mg2+‐containing MOF framework, the composite system retains a portion of its CO2 adsorption capacity while continuing to deliver catalytic activity. The approach is thus critical for designing materials that can bridge the gap between carbon capture and CO2 utilization.

Combining Single Molecule Super-Resolution Imaging Techniques to Unravel the Nanoscale Organization of the Presynapse.

The fusion of synaptic vesicles with the plasma membrane underpins neurotransmission. A number of presynaptic proteins play a critical role in overcoming the energy barrier inherent to the fusion of the negatively charged vesicular and plasma membranes. Emerging concepts suggest that this process is hierarchical and dependent on rapid and transient reorganization of proteins in and out of small nanoclusters located in the active zones of nerve terminals. Examining the nanoscale organization of presynaptic molecules requires super-resolution microscopy to overcome the limits of conventional light microscopy. In this chapter, we describe three super-resolution techniques that allow for the examination of the nanoscale organization of proteins within live hippocampal nerve terminals. We used (1) single-particle tracking photoactivated localization microscopy (sptPALM) to resolve the mobility and clustering of syntaxin1A (STX1A), (2) universal Point Accumulation Imaging in Nanoscale Topography (uPAINT) to study the mobility of a pool of vesicular-associated membrane protein 2 (VAMP2) transiting on the plasma membrane, and (3) subdiffractional Tracking of Internalized Molecules (sdTIM) to track VAMP2-positive recycling synaptic vesicles in conjunction with Cholera Toxin subunit B (CTB), which has recently been shown to be trafficked retrogradely from the presynapse to the cell body via signaling endosomes.

Size- and temperature-dependent magnetization of iron nanoclusters

The magnetic behavior of bcc iron nanoclusters, with diameters between 2 and 8 nm, is investigated by means of spin dynamics (SD) simulations coupled to molecular dynamics (MD-SD), using a distance-dependent exchange interaction. Finite-size effects in the total magnetization as well as the influence of the free surface and the surface/core proportion of the nanoclusters are analyzed in detail for a wide temperature range, going beyond the cluster and bulk Curie temperatures. Comparison is made with experimental data and with theoretical models based on the mean-field Ising model adapted to small clusters, and taking into account the influence of low coordinated spins at free surfaces. Our results for the temperature dependence of the average magnetization per atom M(T), including the thermalization of the transnational lattice degrees of freedom, are in very good agreement with available experimental measurements on small Fe nanoclusters. In contrast, significant discrepancies with experiment are observed if the translational degrees of freedom are artificially frozen. The finite-size effects on M(T) are found to be particularly important near the cluster Curie temperature. Simulated magnetization above the Curie temperature scales with cluster size as predicted by models assuming short-range magnetic ordering (SRMO). Analytical approximations to the magnetization as a function of temperature and size are proposed.

Passivating Nucleobases Bring Charge Transfer Character to Optically Active Transitions in Small Silver Nanoclusters.

DNA-wrapped silver nanoclusters (DNA-AgNCs) are known for their efficient luminescence. However, their emission is highly sensitive to the DNA sequence, the cluster size, and its charge state. To get better insights into photophysics of these hybrid systems, simulations based on density functional theory (DFT) are performed. Our calculations elucidate the effect of the structural conformations, charges, solvent polarity, and passivating bases on optical spectra of DNA-AgNCs containing five and six Ag atoms. It is found that inclusion of water in calculations as a polar solvent media results in stabilization of nonplanar conformations of base-passivated clusters, while their planar conformations are more stable in vacuum, similar to the bare Ag5 and Ag6 clusters. Cytosines and guanines interact with the cluster twice stronger than thymines, due to their larger dipole moments. In addition to the base-cluster interactions, hydrogen bonds between bases notably contribute to the structure stabilization. While the relative intensity, line width, and the energy of absorption peaks are slightly changing depending on the cluster charge, conformations, and base types, the overall spectral shape with five well-resolved bands at 2.5-5.5 eV is consistent for all structures. Independent of the passivating bases and the cluster size and charge, the low energy optical transitions at 2.5-3.5 eV exhibit a metal to ligand charge transfer (MLCT) character with the main contribution emerging from Ag-core to the bases. Cytosines facilitate the MLCT character to a larger degree comparing to the other bases. However, the doublet transitions in clusters with the open shell electronic structure (Ag5 and Ag6+) result in appearance of additional red-shifted (<2.5 eV) and optically weak band with negligible MLCT character. The passivated clusters with the closed shell electronic structure (Ag5+ and Ag6) exhibit higher optical intensity of their lowest transitions with much higher MLCT contribution, thus having better potential for emission, than their open shell counterparts.

Quantitative Evaluation of Spinodal Decomposition in Thermally Aged Binary Fe-35 At.% Cr Alloys by Correlative APT and SANS Analyses

In this work, spinodal decomposition (SD) in Fe-35 at.% Cr alloy is quantified by correlatively combining two complimentary techniques namely, Atom Probe Tomography (APT) and Small Angle Neutron Scattering (SANS). In order to overcome the uncertainty often encountered in quantification of the characteristic SD parameters (wavelength λSD , amplitude A and volume fraction of Cr-rich α/ -phase Φ), we adopt the following: (i) utilize the unique specific attribute of a technique suitable for evaluating any particular SD parameter; (ii) incorporate such reliably extracted parameter as input for evaluating other parameters wherever applicable. This novel correlative approach builds on each other’s strength and provides improved accuracy. λSD is determined independently from APT and SANS analyses. For evaluation of A and Φ, APT analysis utilizes the value of λSD determined from SANS, whereas the phase compositions evaluated by APT are utilized in SANS analysis. With progressive phase separation, α/α/ compositional difference increases continually (from 19.8% after 10 h to 48.2% after 500 h) along with concomitant contraction of the interface (from 1.92 nm to 1.55 nm), underscoring the distinctive characteristics of SD process. Signature of rarely observed early stage of phase separation in the form of a dense population (9.78x1024 /m3 ) of extremely small (0.67 nm radius) Cr-rich nanoclusters is registered after aging only for 1 h. In addition, temporal evolution of λSD clearly distinguishes early stage of SD (time exponent of 0.15) from the coarsening stage (time exponent of 0.29, 120 h onwards).

Hydrotalcite-Supported Ag/Pd Bimetallic Nanoclusters Catalyzed Oxidation and One-Pot Aldol Reaction in Water

A highly active hydrotalcite-supported Ag/Pd bimetallic nanocluster catalyst has been developed by a simple, easy and safe chemical reduction method. The catalyst was characterized by high-resolution transmission electron microscopy (HR-TEM), which revealed very small (3.2 ± 0.7 nm) nanoclusters with a narrow size distribution. The bimetallic Ag/Pd catalyst showed strong cooperation between Ag and Pd for the alcohol oxidation reaction. The developed catalyst provided an efficient and environmentally friendly method for alcohol oxidation and one-pot cross-aldol condensation in water. A broad scope of α,β-unsaturated ketones with good to excellent yields were obtained under very mild conditions. This catalytic system offers an easy preparation method with a simple recovery process, good activity and reusability of up to five cycles without significant loss in the catalytic activity.

Spectroscopic and luminescent properties of the lithium tetraborate glass co-doped with Nd and Ag

Spectroscopic and luminescent properties of the Nd-doped and Nd–Ag co-doped borate glasses with Li2B4O7 (Li2O–2B2O3) basic composition are investigated and analysed using optical absorption, electron paramagnetic resonance (EPR), photoluminescence (excitation, emission, decay kinetics) experimental methods and Judd–Ofelt analysis. Optical absorption, photoluminescence spectra and decay kinetics of Nd3+ ions were registered and detailed analysed. Experimental and theoretical oscillator strengths (fexp and ftheor), Judd–Ofelt intensity parameters (Ω2, Ω4, Ω6), and important to laser applications radiative parameters such as probabilities of radiative transitions (Arad), branching ratios of luminescence (β), radiative lifetimes (τrad), emission cross-sections (σem), and quantum efficiency (η) of the Nd3+ luminescence in the Li2B4O7:Nd and Li2B4O7:Nd,Ag glasses have been calculated. Broad absorption band of surface plasmon resonance (SPR) related to silver nanoparticles was observed in the Li2B4O7:Nd,Ag glass. Presence of the Ag paramagnetic centres and aggregates in the Li2B4O7:Nd,Ag glass was confirmed by EPR spectroscopy. Photoluminescence emission and excitation spectra as well as decay kinetics of the Ag+ ions and small non-plasmonic Ag aggregates or nanoclusters were registered and discussed. Observed enhancement of the Nd3+ luminescence intensity in the Li2B4O7:Nd,Ag glass is explained by effects induced by SPR of the Ag nanoparticles as wells energy transfer from Ag+ ions and Ag aggregates to the Nd3+ ions.

Self-regenerable carbon nanofiber supported Fe – Mo2C catalyst for CH4-CO2 assisted reforming of biomass to hydrogen rich syngas

In-situ self-regenerable Fe / Fe3C – Mo2C – CNF catalyst was developed and evaluated extensively over 15 cycles of CH4 – CO2 assisted biomass reforming. In-situ regeneration was observed through nucleation on carbon saturated Fe3Cx sites due to abundance of free-C from reaction and undercoordinated carbon in support. Molybdenum existed as stable β-Mo2C whereas Fe composition changed from Fe° sites to Fe3Cx. Due to highly dispersed small nanoclusters (< 5 nm) in lower Fe loading catalysts, graphene nanosheets (GNS) synthesis was observed whereas on 5 % Fe catalysts, large agglomerated nanoparticles (∼10 to 20 nm) facilitated CNF / CNT synthesis. Regeneration on 0.5 % Fe occurred through CNF growth while graphene cover regenerated 5 % Fe catalysts. Fe – Mo2C – CNF catalyzed reactions produce hydrogen rich syngas over 15 cycles with H2 concentration > 60 % and H2:CO ratio of 2–4. Hydrodeoxygenation reforming of biomass was typically between 40–60 % of the amount of oxygenates.