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The conversion of biomass to 5-hydroxymethylfurfural (HMF) holds substantial promise as a renewable energy source. Notably, HMF can be transformed into 2,5-bis(hydroxymethyl)furan (BHMF), a crucial reactant in biofuel production, but requires harsh operating conditions, H2, and precious metal catalysts. A recently reported Cannizzaro reaction of HMF to BHMF, characterized by its efficiency, mild conditions, and eco-friendliness, instead employed ionic liquids (ILs) to achieve high yields. In this study, combined quantum mechanical and molecular mechanical (QM/MM) simulations in conjunction with Metropolis Monte Carlo statistical mechanics and free-energy perturbation theory utilized M06-2X/6-31+G(d), PDDG/PM3, and the OPLS-VSIL force field to uncover important solute–solvent interactions present in the HMF to BHMF reaction pathway. The Cannizzaro reaction was examined in water and in five ILs composed of the 1-butyl-3-methylimidazolium [BMIM] cation coupled to hexafluorophosphate, tetrafluoroborate, thiocyanate, chloride, and bromide. Energetic and structural analysis of the rate-determining hydride transfer between HMF and the hydride-donor anion HMFOH− attributed the enhanced reactivity to highly organized solvent interactions featuring (1) hydrogen bonding between the ring protons of [BMIM] and the negatively charged carbonyl oxygen atoms on the transition structure, (2) favorable electrostatic interactions between the IL anions and solute hydroxyl groups, and (3) beneficial π–π stacking interactions between [BMIM] and the two aromatic rings present in HMF and HMFOH−. [ABSTRACT FROM AUTHOR]

Zeolitic Imidazolate Frameworks-8 (ZIF-8) is commonly used as an ideal precursor for non-noble metal catalysts because of its high specific surface area, ultra-high porosity, and N-rich content. Upon pyrolyzing ZIF-8 at 900 °C in Ar, the resulting material, referred to as Z8, displayed good activity toward the oxygen reduction reaction (ORR). Then the ZIF-8 was mixed with various conductive carbon materials, such as multiwall carbon nanotubes (MWCNTs), Acetylene black (ACET), Vulcan XC-72R (XC-72R), and Ketjenblack EC-600JD (EC-600JD), to form Z8 composites. The Z8/MWCNTs composite exhibited enhanced ORR activity owing to its network structure, meso-/microporous hierarchical porous structure, improved electrical conductivity, and graphitization. Subsequently, iron and nitrogen co-doping is achieved through the pyrolysis of a mixture comprising Fe, N precursor, and ZIF-8/MWCNTs, which is denoted as FeN-Z8/MWCNTs. The intrinsically high electrical conductivity of MWCNTs facilitated efficient electron transfer during the ORR, while the meso-/microporous hierarchical porous structure and network structure of Fe, N co-doped ZIF-8/MWCNTs promoted oxygen transport. The presence of Fe-containing species in the catalyst acted as activity centers for ORR. This strategy of preparing Z8 composites and modifying them with Fe, N co-doping offers an insightful approach to designing cost-effective electrocatalysts. [ABSTRACT FROM AUTHOR]

Surface property modification of catalyst support is a straightforward approach to optimize the performance of supported noble metal catalysts. In particular, oxygen vacancies and hydroxyl groups play significant roles in promoting noble metal dispersion on catalysts as well as catalytic stability. In this study, we developed a nanoflower-like TiO2-supported Pd catalyst that has a higher concentration of oxygen vacancies and surface hydroxyl groups compared to that of commercial anatase and P25 support. Notably, due to the distinctive structure of the nanoflower-like TiO2, our catalyst exhibited improved dispersion and stabilization of Pd species and the formation of abundant reactive oxygen species, thereby facilitating the activation of CO and O2 molecules. As a result, the catalyst showed remarkable efficiency in catalyzing the low-temperature CO oxidation reaction with a complete CO conversion at 80 °C and stability for over 100 h. [ABSTRACT FROM AUTHOR]

Magnetic field effects have received widespread attention due to their ability to enhance the process of water splitting at multiple scales. However, a systematic and comprehensive understanding of the source of the magnetic effect and the magnetic modulation of magnetic catalysts is lacking. This perspective focuses on recent advancements in harnessing external magnetic field to improve electrocatalytic water splitting and suggests future directions. First, the mechanism of several magnetic effects and their effects on water splitting are elaborated in detail, including the magnetohydrodynamic effect, magnetothermal effect, spin polarization effect, and magnetoresistance effect. Then, the classification and construction strategies of magnetic effect catalysts are summarized, primarily divided into single metal/alloy catalysts, metal oxide-based catalysts, and other magnetic catalysts. Finally, the challenges and potential perspective of magnetic field-enhanced water splitting are discussed, including mechanism study, in situ characterization, and multi-field synergy effects. [ABSTRACT FROM AUTHOR]

We systematically explored NO activation at metal/oxide interfaces by the combination of Sr3Ti2O7, Sr3Fe2O7, CeO2, anatase-TiO2, ZrO2, and γ-Al2O3 supports and the platinum-group metal cluster (Pd4, Pt4, and Rh4) using slab-model density functional theory calculations. These metal clusters can be strongly adsorbed at these metal oxide surfaces. The Pt4 and Rh4 clusters show larger adsorption energies than the Pd4 cluster, yet the γ-Al2O3(100) surface shows smaller adsorption energies than other metal oxide surfaces. One oxygen vacancy close to the metal cluster was constructed to evaluate the NO activation at those metal/oxide interfaces. The O atom of NO refills the oxygen vacancy after NO dissociation, while the N adatom is left on the metal cluster. The exothermic process was identified for the NO activation except for the Sr3Fe2O7 case, indicating the significant role of the interplay between the metal cluster and oxygen vacancy. [ABSTRACT FROM AUTHOR]

Deposition-precipitation (DP) method is commonly used to prepare the supported metal catalysts. In this study, the modification effect of the mild DP method on the photocatalytic performance of TiO2 was investigated. The TiO2 samples with DP treatment, as well as Au/TiO2 prepared under the same conditions, showed enhanced photocatalytic performance of the degradation of methylene blue (MB). · OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) show that TiO2(A)-17 after DP treatment has the most amount of surface OH ad − species. The presence of surface OH ad − species not only changes the surface zeta potential, favoring the attraction of cationic MB; but also depresses the electron-hole recombination, favoring photodegradation of MB by hole-produced • OH. An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods. [ABSTRACT FROM AUTHOR]

The effect of gases on the surface composition of Cu–Pt bimetallic catalysts has been tested by in situ infrared (IR) and x-ray absorption spectroscopies. Diffusion of Pt atoms within the Cu–Pt nanoparticles was observed both in vacuum and under gaseous atmospheres. Vacuum IR spectra of CO adsorbed on CuPtx/SBA-15 catalysts (x = 0–∞) at 125 K showed no bonding on Pt regardless of Pt content, but reversible Pt segregation to the surface was seen with the high-Pt-content (x ≥ 0.2) samples upon heating to 225 K. In situ IR spectra in CO atmospheres also highlighted the reversible segregation of Pt to the surface and its diffusion back into the bulk when cycling the temperature from 295 to 495 K and back, most evidently for diluted single-atom alloy catalysts (x ≤ 0.01). Similar behavior was possibly observed under H2 using small amounts of CO as a probe molecule. In situ x-ray absorption near-edge structure data obtained for CuPt0.2/SBA-15 under both CO and He pointed to the metallic nature of the Pt atoms irrespective of gas or temperature, but analysis of the extended x-ray absorption fine structure identified a change in coordination environment around the Pt atoms, from a (Pt–Cu):(Pt–Pt) coordination number ratio of ∼6:6 at or below 445 K to 8:4 at 495 K. The main conclusion is that Cu–Pt bimetallic catalysts are dynamic, with the composition of their surfaces being dependent on temperature in gaseous environments. [ABSTRACT FROM AUTHOR]

After Chemical Vapor Deposition (CVD), faceted structures are routinely observed on a variety of metal catalyst surfaces in the graphene-covered regions. In spite of having its bare surface flattened through high diffusivity and surface pre-melting at high temperatures, the graphene-covered copper surface still presents faceted structures. Using atomistic simulations, we show the role of graphene in the preservation of the faceted surface morphology at the graphene–copper interface, manifesting as a suppressant against surface melting and surface-specific diffusion. The results of our molecular dynamics simulations are consistent with our experimental observations and demonstrate the thermo-mechanical interfacial surface stabilization role of graphene. Our study provides an understanding applicable to most metal–graphene interfaces and is especially relevant to most metallic catalysts for graphene growth by CVD. Understanding the interaction between graphene and the catalyst surface structure is critical for producing ultra-flat and defect-free graphene. [ABSTRACT FROM AUTHOR]

The synergy between catalysis and plasma chemistry often enhances the yield of chemical reactions in plasma-driven reactors. In the case of CO2 splitting into CO and O2, no positive synergistic effect was observed in earlier studies with plasma reactors, except for dielectric barrier discharges, that do not have a high yield and a high efficiency. Here, we demonstrate that introducing metal meshes into radio frequency-driven plasma reactors increases the relative reaction yield by 20%–50%, while supported metal oxide catalysts in the same setups have no effect. We attribute this to the double role of the metal mesh, which acts both as a catalyst for direct CO2 dissociation as well as for oxygen recombination. [ABSTRACT FROM AUTHOR]

Supported single-atom catalysts (SACs) have gained increasing attention for improved catalytic activity and selectivity for industrially relevant reactions. In this study, we explore the hydrogenation of acetylene over single Pt, Ru, Rh, Pd, and Ir atoms supported on the Fe3O4(001) surface using density functional theory calculations. The thermodynamic profile of H diffusion is significantly modified by the type of single metal atoms used, suggesting that H spillover from the single atom dopant to the Fe3O4(001) surface is favored and will likely lead to high H coverages of the functioning catalyst. Correspondingly, as the surface H coverage increases, the important desorption step of ethylene becomes energetically competitive against the detrimental hydrogenation steps of ethylene to ethane. A kinetic model is employed to explore how the activity and selectivity of SACs toward ethylene production change as a function of mass of the catalyst loaded into a flow reactor. Overall, we show that the selectivity of SACs toward ethylene production can be tuned by considering the proper type of metal and controlling the redox state of the support. [ABSTRACT FROM AUTHOR]

The catalytic properties of metal oxides are often enabled by surface defects, and their characterization is thus vital to the understanding and application of metal oxide catalysts. Typically, surface defects for metal oxides show fingerprints in spectroscopic characterization. However, we found that synchrotron-radiation photoelectron spectroscopy (SRPES) is difficult to probe surface defects of ZnO. Meanwhile, CO as a probe molecule cannot be used properly to identify surface defect sites on ZnO in infrared (IR) spectroscopy. Instead, we found that formaldehyde could serve as a probe molecule, which is sensitive to surface defect sites and could titrate surface oxygen vacancies on ZnO, as evidenced in both SRPES and IR characterization. Density functional theory calculations revealed that formaldehyde dissociates to form formate species on the stoichiometric ZnO (10 1 ¯ 0) surface, while it dissociates to formyl species on Vo sites of the reduced ZnO (10 1 ¯ 0) surface instead. Furthermore, the mechanism of formaldehyde dehydrogenation on ZnO surfaces was also elucidated, while the generated hydrogen atoms are found to be stored in ZnO bulk from 423 K to 773 K, making ZnO an interesting (de)hydrogenation catalyst. [ABSTRACT FROM AUTHOR]

Indium oxide has received attention as an exciting candidate for catalyzing the CO2 hydrogenation to methanol due to its high selectivity (>80%). Compared to the extent of research on the activity of indium oxide-based powder catalysts, very little is known about the phenomena associated with the formation of surface alloys involving indium or the growth mechanism for indium oxide nanoparticles. In this report, scanning tunneling microscopy and X-ray photoelectron spectroscopy (XPS) were employed to elucidate the growth mode, structure, and chemical state of In/Au(111) alloys and InOx/Au(111) inverse model catalysts. Our study reveals distinct morphological differences between In/Au(111) and InOx/Au(111), and the InOx structure also depends strongly on the preparation conditions. In/Au surface alloy systems with extremely low coverage (0.02 ML) form islands preferentially on the elbow sites of reconstructed Au(111) herringbone, regardless of hexagonally closed packed and face centered cubic stacking. At higher coverage (0.1 ML), the In islands expand over the herringbone in the ⟨110⟩ direction and create two dimensional domain structures over the entire surfaces. Moreover, this 2D domain structure is disturbed by temperature with high dispersion of indium atoms observed during the annealing process. Oxidation of the In/Au(111) surface alloys with O2 at 550 K produces InOx/Au(111) systems which contain various sizes of InOx aggregates (from 0.7 nm to 10 nm). On the other hand, InOx/Au(111) surfaces prepared by vapor deposition of In at 550 K in an O2 background exhibit highly dispersed and uniformly small InOx particles (∼1 nm). Both InOx systems were confirmed to be partially oxidized by XPS. [ABSTRACT FROM AUTHOR]

Signal Amplification by Reversible Exchange (SABRE) is an inexpensive and simple hyperpolarization technique that is capable of boosting nuclear magnetic resonance sensitivity by several orders of magnitude. It utilizes the reversible binding of para-hydrogen, as hydride ligands, and a substrate of interest to a metal catalyst to allow for polarization transfer from para-hydrogen into substrate nuclear spins. While the resulting nuclear spin populations can be dramatically larger than those normally created, their lifetime sets a strict upper limit on the experimental timeframe. Consequently, short nuclear spin lifetimes are a challenge for hyperpolarized metabolic imaging. In this report, we demonstrate how both hyperpolarization and long nuclear spin lifetime can be simultaneously achieved in nitrogen-15 containing derivatives of pyridazine and phthalazine by SABRE. These substrates were chosen to reflect two distinct classes of 15N2-coupled species that differ according to their chemical symmetry and thereby achieve different nuclear spin lifetimes. The pyridazine derivative proves to exhibit a signal lifetime of ∼2.5 min and can be produced with a signal enhancement of ∼2700. In contrast, while the phthalazine derivative yields a superior 15 000-fold 15N signal enhancement at 11.7 T, it has a much shorter signal lifetime. [ABSTRACT FROM AUTHOR]

It is frequently desired to synthesize supported metal catalysts that consist of very small clusters or single atoms. In this work, we combine strong electrostatic adsorption (SEA) of H2PtCl6 and engineered oxide supports to ultimately produce very small Pt clusters, including a large fraction of single Pt atoms. The supports are synthesized by depositing controlled amounts of SiO2 onto Al2O3 (SiO2@Al2O3) that has been previously grafted with bulky organic templates. After the templates are removed, the oxide supports are largely negatively charged, like SiO2, but have small patches of positively charged Al2O3, derived from the regions previously covered by the template. The overall point of zero charge of these materials decreases from pH 6.4 for 1 cycle of SiO2 deposition to a SiO2-like <2 for materials with more than 5 cycles of SiO2 deposition. SEA at pH 4 on templated SiO2@Al2O3 deposits from 1 wt. % to 0.05 wt. % Pt as the amount of SiO2 increases. Pt loadings drop to near zero in the absence of a template. The resulting Pt nanoparticles are generally <1 nm and have dispersion near 100% by CO chemisorption. Finally, CO DRIFTS shows that the CO nanoparticles become increasingly well defined and have a higher percentage of Pt single atoms as the amount of SiO2 increases on the SiO2@Al2O3 particles. Overall, this method of synthesizing patches of charge on a carrier particle appears to be a viable route to creating extremely highly dispersed supported metal catalysts. [ABSTRACT FROM AUTHOR]

Rational engineering of non-noble metal catalysts with exposed highly active facets for water splitting is desirable yet remains greatly challenging. Herein, we report a doping-induced facet transformation strategy to prepare single-crystalline cobalt carbonate hydroxide hydrate (CCOH) nanowires with high oxygen evolution reaction (OER) activity. Specifically, Cu doping induces the CCOH nanowires to grow along the (020) direction, whereas nanowires without Cu dopant grow along the (121) direction. Density functional theory calculations reveal that compared with the (121) surface, the (020) surface of CCOH has higher intrinsic OER activity due to different atomic arrangements and coordination. As a result, the Cu-doped (020)-faceted CCOH nanowire arrays exhibit outstanding OER performances with a low overpotential of 210 mV at 10 mA cm−2 and a Tafel slope of 67 mV dec−1 in alkaline medium, as well as extremely long-term durability over 36 h. Our findings demonstrate that doping-induced facet engineering is an effective strategy to design and develop highly active catalysts. [ABSTRACT FROM AUTHOR]

To understand the mechanism of the H–D exchange reaction for synthesizing various deuterium-labeled molecules on heterogeneous metal catalysts as a first step, we analyzed the effects of H/D isotopes on the adsorption of H2O/D2O and their dissociated OH/OD and H/D species on the Pt(111) surface. We applied the combined plane-wave and localized basis set method developed by us to directly treat the electronic structures of the surface and the localized adsorbed region and the nuclear quantum effect of H and D. The results showed that the adsorption energies for the D-compounds on the Pt surface were larger than those for the H-compounds. This is in keeping with the experimental observations. The difference in the distance between the adsorbates and the Pt surface induced by the H/D isotope effect depends on the bonding characteristics. While the distance between D2O and the Pt surface was longer than that in the H2O case, the distance between the D atom and the Pt surface was shorter than that for the H atom. This is the first report on the geometrical differences between H and D based on a systematic analysis of water and its dissociated species. [ABSTRACT FROM AUTHOR]

Direct methanol fuel cells (DMFCs) are energy carriers with a significant high energy density, easy implementation, a low operating temperature, and a convenient methanol fuel storage, rendering them a reasonable alternative for portable applications. However, there are several substantial barriers to the widespread use of DMFCs that must be addressed. Noble metal-based catalysts have long been regarded as outstanding electrocatalysts for fuel cells, but their high cost and low durability have kept them from becoming widely used. Nickel-based electrocatalysts are possible replacements for expensive noble metal catalysts owing to their low price, high durability, and remarkable surface oxidation properties. Herein, we develop an incredibly active and remarkably stable electrocatalyst for the methanol oxidation reaction (MOR) via a simple hydrothermal method coupled with nitridation to prepare highly porous Ni3N nanosheets arrays supported by nickel foam (NF) substrate. The in situ growth of highly porous nanosheets on NF (NSAs/NF) exposes more active sites and allows fast charge/mass transfer, creating synergistic effects between Ni3N and NF. As a result, the strong interaction between Ni3N and NF prevents leaching and renders the catalyst highly stable for over 20 h with a 72.58% retention rate, making it among the best retention rates reported recently for comparable Ni-based catalysts. Based on these findings, nickel nitride appears to be an excellent electrocatalyst for fuel cell applications. [ABSTRACT FROM AUTHOR]

Shorter chain alcohols, as opposed to longer ones, are beneficial as biomass feedstock for chemicals and fuels, including hydrogen production. More so, it has been demonstrated that carbon–carbon rather than carbon–oxygen bond-cleaving activity determines the product selectivity of a metal catalyst for higher oxygenates reforming. In this report, we investigate the direct C2–C3 bond-cleaving activity of xylitol via first-principles, periodic density functional theory calculations to identify the differences in activities between single-crystal catalysts (SCCs) and single-atom catalysts (SACs). A comparison of the kinetic barriers revealed that xylitol's C–C bond scission appears to be a near-impossible task on SCCs. However, SACs demonstrated higher performance. For example, Ir1/MgO and Ir1/MgO_Ovac (having surface oxygen vacancy) yielded ∼72% and 54% decrease, respectively, in Gibb's free activation energy compared to Ir (111) at the xylitol reforming operating temperature of 473 K. Furthermore, electronic structure calculations revealed an up-shift in the DOS for the surface M1 atoms in all investigated SACs compared to the surface atoms of their respective SCCs, resulting in M1 higher d-band center and stronger adsorbate (s) binding. This study highlights the importance of SACs for boosting the atom efficiency of costly metals while also offering a new strategy for tuning the activity of catalytic reactions. [ABSTRACT FROM AUTHOR]

Defying the isotropic nature of traditional chemical etch, metal-assisted chemical etching (MacEtch) has allowed spatially defined anisotropic etching by using patterned metal catalyst films to locally enhance the etch rate of various semiconductors. Significant progress has been made on achieving unprecedented aspect ratio nanostructures using this facile approach, mostly in solution. However, the path to manufacturing scalability remains challenging because of the difficulties in controlling etch morphology (e.g., porosity and aggregation) and etch rate uniformity over a large area. Here, we report the first programmable vapor-phase MacEtch (VP-MacEtch) approach, with independent control of the etchant flow rates, injection and pulse time, and chamber pressure. In addition, another degree of freedom, light irradiation is integrated to allow photo-enhanced VP-MacEtch. Various silicon nanostructures are demonstrated with each of these parameters systematically varied synchronously or asynchronously, positioning MacEtch as a manufacturing technique for versatile arrays of three-dimensional silicon nanostructures. This work represents a critical step or a major milestone in the development of silicon MacEtch technology and also establishes the foundation for VP-MacEtch of compound semiconductors and related heterojunctions, for lasting impact on damage-free 3D electronic, photonic, quantum, and biomedical devices. [ABSTRACT FROM AUTHOR]

Heterogeneous catalysis on supported and nonsupported nanoparticles is of fundamental importance in the energy and chemical conversion industries. Rather than laboratory analysis, first-principles calculations give us an atomic-level understanding of the structure and reactivity of nanoparticles and supports, greatly reducing the efforts of screening and design. However, unlike catalysis on low index single crystalline surfaces, nanoparticle catalysis relies on the tandem properties of a support material as well as the metal cluster itself, often with charge transfer processes being of key importance. In this perspective, we examine current state-of-the-art quantum-chemical research for the modeling of reactions that utilize small transition metal clusters on metal oxide supports. This should provide readers with useful insights when dealing with chemical reactions on such systems, before discussing the possibilities and challenges in the field. [ABSTRACT FROM AUTHOR]

The atomistic simulation of supported metal catalysts has long been challenging due to the increased complexity of dual components. In order to determine the metal/support interface, efficient theoretical tools to map out the potential energy surface (PES) are generally required. This work represents the first attempt to apply the recently developed SSW-NN method, stochastic surface walking (SSW) global optimization based on global neural network potential (G-NN), to explore the PES of a highly controversial supported metal catalyst, Au/CeO2, system. By establishing the ternary Au–Ce–O G-NN potential based on first principles global dataset, we have searched for the global minima for a series of Au/CeO2 systems. The segregation and diffusion pathway for Au clusters on CeO2(111) are then explored by using enhanced molecular dynamics. Our results show that the ultrasmall cationic Au clusters, e.g., Au4O2, attaching to surface structural defects are the only stable structural pattern and the other clusters on different CeO2 surfaces all have a strong energy preference to grow into a bulky Au metal. Despite the thermodynamics tendency of sintering, Au clusters on CeO2 have a high kinetics barrier (>1.4 eV) in segregation and diffusion. The high thermodynamics stability of ultrasmall cationic Au clusters and the high kinetics stability for Au clusters on CeO2 are thus the origin for the high activity of Au/CeO2 catalysts in a range of low temperature catalytic reactions. We demonstrate that the global PES exploration is critical for understanding the morphology and kinetics of metal clusters on oxide support, which now can be realized via the SSW-NN method. [ABSTRACT FROM AUTHOR]

Metal oxide supports often play an active part in heterogeneous catalysis by moderating both the structure and the electronic properties of the metallic catalyst particle. In order to provide some fundamental understanding on these effects, we present here a density functional theory (DFT) investigation of the binding of O and CO on Pt nanoparticles supported on titania (anatase) surfaces. These systems are complex, and in order to develop realistic models, here, we needed to perform DFT calculations with up to ∼1000 atoms. By performing full geometry relaxations at each stage, we avoid any effects of "frozen geometry" approximations. In terms of the interaction of the Pt nanoparticles with the support, we find that the surface deformation of the anatase support contributes greatly to the adsorption of each nanoparticle, especially for the anatase (001) facet. We attempt to separate geometric and electronic effects and find a larger contribution to ligand binding energy arising from the former. Overall, we show an average weakening (compared to the isolated nanoparticle) of ∼0.1 eV across atop, bridge and hollow binding sites on supported Pt55 for O and CO, and a preservation of site preference. Stronger effects are seen for O on Pt13, which is heavily deformed by anatase supports. In order to rationalize our results and examine methods for faster characterization of metal catalysts, we make use of electronic descriptors, including the d-band center and an electronic density based descriptor. We expect that the approach followed in this study could be applied to study other supported metal catalysts. [ABSTRACT FROM AUTHOR]

The influence of alloying on mode-selectivity in H2O dissociation on Cu/Ni bimetallic surfaces has been studied using a fully quantum approach based on reaction path Hamiltonian. Both the metal alloy catalyst surface and the normal modes of H2O impact the chemical reactivity of H2O dissociation. A combination of these two different factors will enhance their influence reasonably. Among all the bimetallic surfaces, one monolayer (Ni4_Cu(111)) and 1 2 monolayer of Ni on Cu surface (Ni2_Cu(111)) show lowest barrier to the dissociation. Excitation of bending mode and symmetric stretching mode enhances the reactivity remarkably due to a significant decrease in their frequencies near the transition state in the vibrational adiabatic approximation. In the presence of non-adiabatic coupling between the modes, asymmetric stretching also shows similar enhancement in reactivity to that of symmetric stretching for all the systems. Inclusion of lattice motion using a sudden model enhances the dissociation probability at surface temperature 300 K and at lower incident energy, compared to that of the static surface approximation. The mode selective behaviour of H2O molecules is almost similar on all the Cu- and Ni-based surfaces. The excitation of symmetric stretching vibration by one quantum is shown to have largest efficacy for promoting reactions for all the systems. Overall, the dissociation probabilities for all the systems are enhanced by vibrational excitation of normal modes and become more significant with the non-adiabatic coupling effect. [ABSTRACT FROM AUTHOR]

The industrial pollutant NO is a potential threat to the environment and to human health. Thus, selective catalytic reduction of NO into harmless N2, NH3, and/or N2O gas is of great interest. Among many catalysts, metal Pd has been demonstrated to be most efficient for selectivity of reducing NO to N2. However, the reduction mechanism of NO on Pd, especially the route of N−N bond formation, remains unclear, impeding the development of new, improved catalysts. We report here the elementary reaction steps in the reaction pathway of reducing NO to NH3, N2O, and N2, based on density functional theory (DFT)-based quantum mechanics calculations. We show that the formation of N2O proceeds through an Eley-Rideal (E−R) reaction pathway that couples one adsorbed NO* with one non−adsorbed NO from the solvent or gas phase. This reaction requires high NO* surface coverage, leading first to the formation of the trans-(NO)2* intermediate with a low N−N coupling barrier (0.58 eV). Notably, trans-(NO)2* will continue to react with NO in the solvent to form N2O, that has not been reported. With the consumption of NO and the formation of N2O* in the solvent, the Langmuir-Hinshelwood (L-H) mechanism will dominate at this time, and N2O* will be reduced by hydrogenation at a low chemical barrier (0.42 eV) to form N2. In contrast, NH3 is completely formed by the L-H reaction, which has a higher chemical barrier (0.87 eV). Our predicted E-R reaction has not previously been reported, but it explains some existing experimental observations. In addition, we examine how catalyst activity might be improved by doping a single metal atom (M) at the NO* adsorption site to form M/Pd and show its influence on the barrier for forming the N−N bond to provide control over the product distribution. [ABSTRACT FROM AUTHOR]

Atomically dispersed metal catalysts have been a research hotspot in the field of nanocatalysis due to their unique advantages in recent years. The isolated single or few atoms can be anchored on supports via chemical bonding or space confinement to maximize atom utilization efficiency, reducing the use of metal resources while displaying distinguished catalytic performance. This perspective presents the latest advances in single-atom site catalysts (SACs) and multi-atom site catalysts (MACs), highlights their superiority, and discusses the current limitations as well as the outlooks facing their future development. [ABSTRACT FROM AUTHOR]

Vertically Aligned Carbon Nanotubes (VACNT) are promising soft materials in advanced devices, including wearable strain sensors. VACNT uniform growth depends on nucleation, growth, and deactivation of metal seed catalysts by chemical vapor deposition (CVD) at specific process conditions. CVD is performed at controlled process conditions to maximize VACNT growth with iron seed catalysts of various sizes, optimize water vapor concentration for enhanced VACNT growth, and probe their morphology by creating competition of the hydrocarbon feedstock to Fe seed catalyst of selected layer thicknesses. The analytical studies include ellipsometry to measure thermal oxide, barrier layer, and catalyst layer thicknesses; Raman spectroscopy to assess the characteristic peaks of carbon nanotubes; as well as scanning electron microscopy to evaluate VACNT morphology. The findings show a maximum VACNT growth of 1284 µm at 1 nm Fe catalyst, optimum water vapor content at 12.5–20 SCCM, and predominantly concaved and corrugated, a tube chamber position-dependent VACNT structures with low Ar/H2 ratio and C2H4 gas rates. [ABSTRACT FROM AUTHOR]

The one-step conversion of ethanol to 1,3-butadiene has achieved a breakthrough with the development of beta zeolite supported dual metal catalysts. However, the reaction mechanism from ethanol to butadiene is complex and has not yet been fully elucidated, and no catalyst screening effort has been done based on central metal atoms. In this work, density functional theory (DFT) calculations were employed to study the mechanism of one-step conversion of ethanol to butadiene over Zn-Y/BEA catalyst. The results show that ethanol dehydrogenation prefers to proceed on Zn site with a reaction energy of 0.77 eV in the rate-determining step, and the aldol condensation to produce butadiene prefers to proceed on Y site with a reaction energy of 0.69 eV in the rate-determining step. Based on the mechanism revealed, six elements were selected to replace Y for screening superior combination of Zn-M/BEA (M=Sn, Nb, Ta, Hf, Zr, Ti; BEA: beta polymorph A) for this reaction. As a result, Zn-Y/BEA (0.69 eV) is proven to be the most preferring catalyst compared with the other six ones, and Zn-Zr/BEA (0.85 eV), Zn-Ti/BEA (0.87 eV), and Zn-Sn/BEA (0.93 eV) can be potential candidates for the conversion of ethanol to butadiene. This work not only provides mechanistic insights into one-step catalytic conversion of ethanol to butadiene over Zn-Y/BEA catalyst but also offers more promising catalyst candidates for this reaction. [ABSTRACT FROM AUTHOR]

The commonly used oxide-supported metal catalysts are usually prepared in aqueous phase, which then often need to undergo calcination before usage. Therefore, the surface hydration and dehydration of oxide supports are critical for the realistic modeling of supported metal catalysts. In this work, by ab initio molecular dynamics (AIMD) simulations, the initial anhydrous monoclinic ZrO2( 1 ¯ 11) surfaces are evaluated within explicit solvents in aqueous phase at mild temperatures. During the simulations, all the two-fold-coordinated O sites will soon be protonated to form the acidic hydroxyls (HOL), remaining the basic hydroxyls (HO*) on Zr. The basic hydroxyls (HO*) can easily diffuse on surfaces via the active proton exchange with the undissociated adsorption water (H2O*). Within the temperatures ranging from 273 K to 373 K, in aqueous phase a certain representative equilibrium hydrated m-ZrO2( 1 ¯ 11) surface is obtained with the coverage (θ) of 0.75 on surface Zr atoms. Later, free energies on the stepwise surface water desorption are calculated by density functional theory to mimic the surface dehydration under the mild calcination temperatures lower than 800 K. By obtaining the phase diagrams of surface dehydration, the representative partially hydrated m-ZrO2( 1 ¯ 11) surfaces (0.25≤θ<0.75) at various calcination temperatures are illustrated. These hydrated m-ZrO2( 1 ¯ 11) surfaces can be crucial and readily applied for more realistic modeling of ZrO2 catalysts and ZrO2-supported metal catalysts. [ABSTRACT FROM AUTHOR]

Here we present an approach for the determination of an atomic structure of small bimetallic nanoparticles by combining extended X-ray absorption fine structure spectroscopy and classical molecular dynamics simulations based on the Sutton-Chen potential. The proposed approach is illustrated in the example of PdAu nanoparticles with ca 100 atoms and narrow size and compositional distributions. Using a direct modeling approach and no adjustable parameters, we were able to reproduce the size and shape of nanoparticles as well as the intra-particle distributions of atoms and metal mixing ratios and to explore the influence of these parameters on the local structure and dynamics in nanoparticles. [ABSTRACT FROM AUTHOR]

Iron(III) oxide (α-Fe2O3) is a known water splitting catalyst commonly used in photoelectrochemical cells. These cells are severely impaired by poor conductivity in α-Fe2O3, and resolving the conductivity issue is therefore crucial. One of the most intrinsic properties of matter, which governs conductivity, is the carrier effective masses. In this work, we investigate the carrier effective masses in α-Fe2O3 and other corundum oxides, including Al2O3, Cr2O3, Ga2O3, and In2O3 with different theoretical constructs: density functional theory (DFT), DFT+U, hybrid DFT, and G0W0. We find DFT sufficiently describes the carrier masses and a quasi-particle theory is only required for accuracies better than 30% for the conduction band effective mass. Additionally, we compare the density of states (DOS) and band effective mass approximations and conclude the DOS effective mass provides poor results whenever the band structure is anisotropic. We find that the charge carriers in Fe2O3 "play the heavy" since they have large effective masses that reduce conductivity and device efficiency. Finally, we conclude that the less heavy electron effective masses of other corundum oxides studied relative to Fe2O3 could contribute to efficiency improvements in Fe2O3 upon Al2O3, Ga2O3, and In2O3 coverage. [ABSTRACT FROM AUTHOR]

While methyl transfer is well known to occur in the enzyme- and metal-catalyzed reactions, the methyl transfer in the metal-free organic molecules induced by the photon ionization has been less concerned. Herein, vacuum ultraviolet single photon ionization and dissociation of ethanol dimer are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical methods. Besides the protonated clusters cation (C2H5OH)·H+ (m/z = 47) and the ß-carbon-carbon bond cleavage fragment CH2O·(C2H5OH)H+ (m/z = 77), the measured mass spectra revealed that a new fragment (C2H5OH)·(CH3)+ (m/z = 61) appeared at the photon energy of 12.1 and 15.0 eV, where the neutral dimer could be vertically ionized to higher ionic state. Thereafter, the generated carbonium ions are followed by a Wagner-Meerwein rearrangement and then dissociate to produce this new fragment, which is considered to generate after surmounting a few barriers including intra- and inter-molecular methyl migrations by the aid of theoretical calculations. The appearance energy of this new fragment is measured as 11.55 ± 0.05 eV by scanning photoionization efficiency curve. While the signal intensity of fragment m/z = 61 starts to increase, the fragments m/z = 47 and 77 tend to slowly incline around 11.55 eV photon energy. This suggests that the additional fragment channels other than (C2H5OH)·H+ and CH2O·(C2H5OH)H+ have also been opened, which consume some dimer cations. The present report provides a clear description of the photoionization and dissociation processes of the ethanol dimer in the range of the photon energy 12-15 eV [ABSTRACT FROM AUTHOR]

The fabrication of alkoxysilane-based nickel (Ni)–palladium (Pd) bimetallic nanoparticle catalysts with several compositions (Pd—0.001M and Ni—0.001–0.1M) was attempted for the first time; these materials were investigated for use as low-cost catalysts in the hydrogen evolution reaction (HER). Functional alkoxysilane [2-(3,4 epoxycyclohexyl)ethyltrimethoxysilane]-assisted conversion of Pd2+ to Pd0 was demonstrated. Palladium nanocrystallites with an average dimension 4.03 ± 1.29 nm were synthesized, which acted as seeds in the synthesis of Ni–Pd bimetallic nanoparticles. The effect of the nanoparticle catalysts on the HER in an alkaline environment was studied using linear sweep voltammetry and electrochemical impedance spectroscopy. A nanostructured thin film containing Ni3PdNPs produced a 100 mA cm−2 current density at an overpotential of −90 mV with a small Tafel slope of 25 mV dec−1 at a catalyst loading of 0.1 mg cm−2. The annealed Ni3PdNPs catalyst further enhanced the current density to ∼ 240 mA cm−2 at an overpotential of −56 mV. [ABSTRACT FROM AUTHOR]

Compared with traditional precious metal catalysts, MoS2 is regarded as the promising hydrogen evolution reaction catalyst for Si photocathodes, because of its higher photochemical stability and lower hydrogen adsorption free energy. However, the layers of MoS2 are connected by van der Waals force, and the interaction force between the layers of MoS2 and Si is weak. Therefore, the homogeneous MoS2 nanosheets directly synthesized on Si by the hydrothermal method remain challenging. Herein, we report a facile strategy for the fast and efficient growth of vertically standing MoS2 on pyramid Si via surface hydrophilicity tailoring by inserting a thin TiO2 layer. Thanks to the improved light trapping and catalytic kinetics, the optimal MoS2/TiO2/Si shows a short-circuit photocurrent density of 9.79 mA/cm2 and an onset potential of 0.31 V vs reversible hydrogen electrode under 100 mW/cm2 Xe‐lamp illumination. By comparing with different oxide buffer layers, surface hydrophilicity is found to be essential for promoting the homogenous nucleation and growth of vertically standing MoS2 by the hydrothermal method. These results not only provide valuable insight into the growth kinetics of transition metal chalcogenides in aqueous solution but also deliver an efficient route for assembling noble-metal free catalysts on silicon-based photoelectrodes. [ABSTRACT FROM AUTHOR]

Creative approaches for designing heterostructures that consist of different dimensional components are necessary for achieving highly efficient catalytic materials. Here, we report an in situ supersaturation-triggered growth of vertically aligned 2D CoFeP nanosheet/1D Fe-CoP nanowire (2D/1D CoFeP NS@Fe-CoP NW) heterostructures with open hierarchical architecture. The integrating 1D nanowires and 2D nanosheets and well-defined 2D–1D interfacial coupling possess enhanced charge transfer, more active sites, and favorable kinetics during electrolysis, resulting in superb electrocatalytic performance for hydrogen evolution reaction, oxygen evolution reaction (OER), and overall water splitting. Specifically, CoFeP NS@Fe-CoP NW heterostructures are efficient OER catalysts in alkaline solution with an overpotential of 250 mV at 30 mA cm−2, outperforming most reported non-noble metal phosphide electrocatalysts. This work provides a facile and scalable strategy to design non-noble metal catalysts with multifunctionality and high activity. [ABSTRACT FROM AUTHOR]

The catalytic growth of Zn3N2 using guided-stream thermal chemical vapor deposition has been investigated within the parameter range of acicular growth to obtain uniform microtips with a high crystalline quality. The cubic anti-bixbyite crystal structure of Zn3N2 microtips and its related phonon mode are revealed by X-ray diffraction and Raman spectroscopy, respectively. The surface morphologies of pure and surface-oxidized Zn3N2 microtips are depicted by scanning electron microscopy and show the crack formation on the surface-oxidized Zn3N2 microtips. The spatial element distribution map confirms the VLS growth mechanism for Zn3N2 microtips and reveals the depth profile of zinc, nitrogen, oxygen, and nickel elements. Photoluminescence (PL) spectra of Zn3N2 microtips show a sharp infrared band-to-band emission peak at 1.34 eV with a full width at half maximum of ~100 meV and a very broad oxygen-related defect band emission peak centered at ~0.85eV [ABSTRACT FROM AUTHOR]

Biomass pyrolysis has become one of the promising technologies for fuel and fine chemical production. Cellulose constitutes the main body of plant biomass and may serve as a stereochemically pure reservoir to obtain active reagents for the synthesis of biologically active substances and structural units of valuable chemical substances. This study investigated the effect of cadmium (Cd) and tin (Sn) modified mesoporous sieve R-MCM-41 (R: Cd or Sn) on the pyrolysis of cellulose via thermogravimetric analysis (TGA) and pyrolysis coupled with gas chromatography/mass spectrometry (Py-GC/MS). The Si/R molar ratio of metal modified catalysts was between 100:1 and 10:1. TGA showed that Cd- and Sn-modified MCM-41 can effectively promote the degradation of cellulose, which was almost completely volatilized at 650 °C under the catalysis of Cd-MCM-41(50) and Sn-MCM-41(50). Py-GC/MS tests were carried out with different R-MCM-41s, reaction temperatures of 450 °C, 550 °C, and 650 °C, and the cellulose-to-catalyst ratios of 5:1, 1:1, and 1:5. The use of Sn-MCM-41 promoted the formation of glycolaldehyde and a limited amount of 1,2-cyclopentanedione and 5-methylfurfural. Cd-MCM-41 catalyzed pyrolysis produced higher levels of 5-hydroxymethylfurfural, 1-hydroxy-3,6-dioxabicyclo[3.2.1]octan-2-one (LAC), 2,5-dimethyl-4-hydroxy-3(2H)-furanone, 2-hydroxy-3-methyl-2-cyclopenten-1-one, 1,2-cyclopentanedione, 3-methyl-2,4(3H,5H)-furandione, furfural, hydroxyacetone, glycolaldehyde, and butanone. When the pyrolysis temperature increased from 450 °C to 650 °C, the content of most small-molecule chemicals in the products increased by 1.8–4.1 times. When applying over-dosage of Cd-MCM-41(50) in the pyrolysis, anhydrosugars were completely degraded and dehydration/decarbonylation reactions were extensively enhanced, resulting in major products of butanone, furfural, and 5-methylfurfural. The possible reaction mechanism was proposed. [ABSTRACT FROM AUTHOR]