Unveiling Highly Sensitive Active Site in Atomically Dispersed Gold Catalysts for Enhanced Ethanol Dehydrogenation.

Developing a desirable ethanol dehydrogenation process necessitates a highly efficient and selective catalyst with low cost. Herein, we show that the "complex active site" consisting of atomically dispersed Au atoms with the neighboring oxygen vacancies (Vo) and undercoordinated cation on oxide supports can be prepared and display unique catalytic properties for ethanol dehydrogenation. The "complex active site" Au-Vo-Zr3+ on Au1/ZrO2 exhibits the highest H2 production rate, with above 37,964 mol H2 per mol Au per hour (385 g H2 g Au - 1 ${{\rm{g}}_{{\rm{Au}}}^{ - 1} }$ h-1) at 350 °C, which is 3.32, 2.94 and 15.0 times higher than Au1/CeO2, Au1/TiO2, and Au1/Al2O3, respectively. Combining experimental and theoretical studies, we demonstrate the structural sensitivity of these complex sites by assessing their selectivity and activity in ethanol dehydrogenation. Our study sheds new light on the design and development of cost-effective and highly efficient catalysts for ethanol dehydrogenation. Fundamentally, atomic-level catalyst design by colocalizing catalytically active metal atoms forming a structure-sensitive "complex site", is a crucial way to advance from heterogeneous catalysis to molecular catalysis. Our study advanced the understanding of the structure sensitivity of the active site in atomically dispersed catalysts.

Atomically synergistic Zn-Cr catalyst for iso-stoichiometric co-conversion of ethane and CO2 to ethylene and CO.

Developing atomically synergistic bifunctional catalysts relies on the creation of colocalized active atoms to facilitate distinct elementary steps in catalytic cycles. Herein, we show that the atomically-synergistic binuclear-site catalyst (ABC) consisting of [Formula: see text]-O-Cr6+ on zeolite SSZ-13 displays unique catalytic properties for iso-stoichiometric co-conversion of ethane and CO2. Ethylene selectivity and utilization of converted CO2 can reach 100 % and 99.0% under 500 °C at ethane conversion of 9.6%, respectively. In-situ/ex-situ spectroscopic studies and DFT calculations reveal atomic synergies between acidic Zn and redox Cr sites. [Formula: see text] ([Formula: see text]) sites facilitate ß-C-H bond cleavage in ethane and the formation of Zn-Hδ- hydride, thereby the enhanced basicity promotes CO2 adsorption/activation and prevents ethane C-C bond scission. The redox Cr site accelerates CO2 dissociation by replenishing lattice oxygen and facilitates H2O formation/desorption. This study presents the advantages of the ABC concept, paving the way for the rational design of novel advanced catalysts.

Ternary NiMo-Bi liquid alloy catalyst for efficient hydrogen production from methane pyrolysis.

Methane pyrolysis (MP) is a potential technology for CO2-free hydrogen production that generates only solid carbon by-products. However, developing a highly efficient catalyst for stable methane pyrolysis at a moderate temperature has been challenging. We present a new and highly efficient catalyst created by modifying a Ni-Bi liquid alloy with the addition of Mo to produce a ternary NiMo-Bi liquid alloy catalyst (LAC). This catalyst exhibited a considerably low activation energy of 81.2 kilojoules per mole, which enabled MP at temperatures between 450 and 800 Celsius and a hydrogen generation efficiency of 4.05 ml per gram of nickel per minute. At 800 Celsius, the catalyst exhibited 100% H2 selectivity and 120 hours of stability.

Formation of active sites on transition metals through reaction-driven migration of surface atoms.

Adopting low-index single-crystal surfaces as models for metal nanoparticle catalysts has been questioned by the experimental findings of adsorbate-induced formation of subnanometer clusters on several single-crystal surfaces. We used density functional theory calculations to elucidate the conditions that lead to cluster formation and show how adatom formation energies enable efficient screening of the conditions required for adsorbate-induced cluster formation. We studied a combination of eight face-centered cubic transition metals and 18 common surface intermediates and identified systems relevant to catalytic reactions, such as carbon monoxide (CO) oxidation and ammonia (NH3) oxidation. We used kinetic Monte Carlo simulations to elucidate the CO-induced cluster formation process on a copper surface. Scanning tunneling microscopy of CO on a nickel (111) surface that contains steps and dislocations points to the structure sensitivity of this phenomenon. Metal-metal bond breaking that leads to the evolution of catalyst structures under realistic reaction conditions occurs much more broadly than previously thought.

Reversible dehydrogenation and rehydrogenation of cyclohexane and methylcyclohexane by single-site platinum catalyst.

Developing highly efficient and reversible hydrogenation-dehydrogenation catalysts shows great promise for hydrogen storage technologies with highly desirable economic and ecological benefits. Herein, we show that reaction sites consisting of single Pt atoms and neighboring oxygen vacancies (VO) can be prepared on CeO2 (Pt1/CeO2) with unique catalytic properties for the reversible dehydrogenation and rehydrogenation of large molecules such as cyclohexane and methylcyclohexane. Specifically, we find that the dehydrogenation rate of cyclohexane and methylcyclohexane on such sites can reach values above 32,000 molH2 molPt-1 h-1, which is 309 times higher than that of conventional supported Pt nanoparticles. Combining of DRIFTS, AP-XPS, EXAFS, and DFT calculations, we show that the Pt1/CeO2 catalyst exhibits a super-synergistic effect between the catalytic Pt atom and its support, involving redox coupling between Pt and Ce ions, enabling adsorption, activation and reaction of large molecules with sufficient versatility to drive abstraction/addition of hydrogen without requiring multiple reaction sites.

Nanoparticle Assembly Induced Ligand Interactions for Enhanced Electrocatalytic CO2 Conversion.

The microenvironment in which the catalysts are situated is as important as the active sites in determining the overall catalytic performance. Recently, it has been found that nanoparticle (NP) surface ligands can actively participate in creating a favorable catalytic microenvironment, as part of the nanoparticle/ordered-ligand interlayer (NOLI), for selective CO2 conversion. However, much of the ligand-ligand interactions presumed essential to the formation of such a catalytic interlayer remains to be understood. Here, by varying the initial size of NPs and utilizing spectroscopic and electrochemical techniques, we show that the assembly of NPs leads to the necessary ligand interactions for the NOLI formation. The large surface curvature of small NPs promotes strong noncovalent interactions between ligands of adjacent NPs through ligand interdigitation. This ensures their collective behavior in electrochemical conditions and gives rise to the structurally ordered ligand layer of the NOLI. Thus, the use of smaller NPs was shown to result in a greater catalytically effective NOLI area associated with desolvated cations and electrostatic stabilization of intermediates, leading to the enhancement of intrinsic CO2-to-CO turnover. Our findings highlight the potential use of tailored microenvironments for NP catalysis by controlling its surface ligand interactions.

Insights into the Mechanism of Methanol Steam Reforming Tandem Reaction over CeO2 Supported Single-Site Catalysts.

We demonstrated how the special synergy between a noble metal single site and neighboring oxygen vacancies provides an "ensemble reaction pool" for high hydrogen generation efficiency and carbon dioxide (CO2) selectivity of a tandem reaction: methanol steam reforming. Specifically, the hydrogen generation rate over single site Ru1/CeO2 catalyst is up to 9360 mol H2 per mol Ru per hour (579 mLH2 gRu-1 s-1) with 99.5% CO2 selectivity. Reaction mechanism study showed that the integration of metal single site and O vacancies facilitated the tandem reaction, which consisted of methanol dehydrogenation, water dissociation, and the subsequent water gas shift (WGS) reaction. In addition, the strength of CO adsorption and the reaction activation energy difference between methanol dehydrogenation and WGS reaction play an important role in determining the activity and CO2 selectivity. Our study paves the way for the further rational design of single site catalysts at the atomic scale. Furthermore, the development of such highly efficient and selective hydrogen evolution systems promises to deliver highly desirable economic and ecological benefits.

Mechanism of Methanol Decomposition over Single-Site Pt1/CeO2 Catalyst: A DRIFTS Study.

Single-site catalysts have drawn broad attention in catalysis because of their maximum atomic utilization and unique catalytic performance. Early work in our group has shown a 40-fold higher activity of methanol decomposition over single-site Pt1/CeO2 catalyst than CeO2 supported 2.5 nm Pt nanoparticles, while a molecular-level understanding of such enhancement is lacking. Herein, the reaction mechanism of methanol decomposition over Pt1/CeO2 was carefully investigated using in situ DRIFTS, and a reaction pathway was proposed. Methanol molecules were dissociatively adsorbed on nanoceria support first, followed by the diffusion of as-formed methoxy species onto Pt single sites where the dehydrogenation occurs and results in the weakly bonded CO. The ease of methanol dissociative adsorption on nanoceria support and the tailored electronic property of Pt1 via the metal-support interaction are believed to be strongly correlated with the high activity of Pt1/CeO2.

Enhanced and stabilized hydrogen production from methanol by ultrasmall Ni nanoclusters immobilized on defect-rich h-BN nanosheets.

Employing liquid organic hydrogen carriers (LOHCs) to transport hydrogen to where it can be utilized relies on methods of efficient chemical dehydrogenation to access this fuel. Therefore, developing effective strategies to optimize the catalytic performance of cheap transition metal-based catalysts in terms of activity and stability for dehydrogenation of LOHCs is a critical challenge. Here, we report the design and synthesis of ultrasmall nickel nanoclusters (∼1.5 nm) deposited on defect-rich boron nitride (BN) nanosheet (Ni/BN) catalysts with higher methanol dehydrogenation activity and selectivity, and greater stability than that of some other transition-metal based catalysts. The interface of the two-dimensional (2D) BN with the metal nanoparticles plays a strong role both in guiding the nucleation and growth of the catalytically active ultrasmall Ni nanoclusters, and further in stabilizing these nanoscale Ni catalysts against poisoning by interactions with the BN substrate. We provide detailed spectroscopy characterizations and density functional theory (DFT) calculations to reveal the origin of the high productivity, high selectivity, and high durability exhibited with the Ni/BN nanocatalyst and elucidate its correlation with nanocluster size and support-nanocluster interactions. This study provides insight into the role that the support material can have both regarding the size control of nanoclusters through immobilization during the nanocluster formation and also during the active catalytic process; this twofold set of insights is significant in advancing the understanding the bottom-up design of high-performance, durable catalytic systems for various catalysis needs.

Insights into the Mechanism of n-Hexane Reforming over a Single-Site Platinum Catalyst.

We demonstrate that the single-site catalyst Pt1/CeO2 greatly enhances the selectivity of cyclization and aromatization in the n-hexane reforming reaction. Specifically, the selectivity of single-site Pt1/CeO2 toward both cyclization and aromatization is above 86% at 350 °C. The turnover frequency of Pt1/CeO2 is 58.8 h-1 at 400 °C, which is close to that of Pt cluster/CeO2 (61.4 h-1) and much higher than that of Pt nanoparticle/CeO2 with Pt sizes of 2.5 and 7 nm. On the basis of the catalytic results for methylcyclopentane reforming, the dehydrocyclization and further aromatization of n-hexane are attributed to the prominent adsorption of ring intermediate products on the single-site Pt1/CeO2 catalysts. On the other side, with the multiple Pt adjacent active sites, the cluster and nanoparticle Pt/CeO2 samples favor the C-C bond cracking reaction. Ultimately, this in-depth study unravels the principles of hydrocarbon activation with different Pt sizes and represents a key step toward the rational design of new heterogeneous catalysts.

Unsaturated Ligands Seed an Order to Disorder Transition in Mixed Ligand Shells of CdSe/CdS Quantum Dots.

A phase transition within the ligand shell of core/shell quantum dots is studied in the prototypical system of colloidal CdSe/CdS quantum dots with a ligand shell composed of bound oleate (OA) and octadecylphosphonate (ODPA). The ligand shell composition is tuned using a ligand exchange procedure and quantified through proton NMR spectroscopy. Temperature-dependent photoluminescence spectroscopy reveals a signature of a phase transition within the organic ligand shell. Surprisingly, the ligand order to disorder phase transition triggers an abrupt increase in the photoluminescence quantum yield (PLQY) and full-width at half-maximum (FWHM) with increasing temperature. The temperature and width of the phase transition show a clear dependence on ligand shell composition, such that QDs with higher ODPA fractions have sharper phase transitions that occur at higher temperatures. In order to gain a molecular understanding of the changes in ligand ordering, Fourier transform infrared and vibrational sum frequency generation spectroscopies are performed. These measurements confirm that an order/disorder transition in the ligand shell tracks with the photoluminescence changes that accompany the ligand phase transition. The phase transition is simulated through a lattice model that suggests that the ligand shell is well-mixed and does not have completely segregated domains of OA and ODPA. Furthermore, we show that the unsaturated chains of OA seed disorder within the ligand shell.

Efficient Hydrogen Production from Methanol Using a Single-Site Pt1/CeO2 Catalyst.

Hydrogen is regarded as an attractive alternative energy carrier due to its high gravimetric energy density and only water production upon combustion. However, due to its low volumetric energy density, there are still some challenges in practical hydrogen storage and transportation. In the past decade, using chemical bonds of liquid organic molecules as hydrogen carriers to generate hydrogen in situ provided a feasible method to potentially solve this problem. Research efforts on liquid organic hydrogen carriers (LOHCs) seek practical carrier systems and advanced catalytic materials that have the potential to reduce costs, increase reaction rate, and provide a more efficient catalytic hydrogen generation/storage process. In this work, we used methanol as a hydrogen carrier to release hydrogen in situ with the single-site Pt1/CeO2 catalyst. Moreover, in this reaction, compared with traditional nanoparticle catalysts, the single site catalyst displays excellent hydrogen generation efficiency, 40 times higher than 2.5 nm Pt/CeO2 sample, and 800 times higher compared to 7.0 nm Pt/CeO2 sample. This in-depth study highlights the benefits of single-site catalysts and paves the way for further rational design of highly efficient catalysts for sustainable energy storage applications.

Oligomerization of Light Olefins Catalyzed by Brønsted-Acidic Metal-Organic Framework-808.

Sulfated metal-organic framework-808 (S-MOF-808) exhibits strong Brønsted-acidic character which makes it a potential candidate for the heterogeneous acid catalysis. Here, we report the isomerization and oligomerization reactions of light olefins (C3-C6) over S-MOF-808 at relatively low temperatures and ambient pressure. Different products (dimers, isomers, and heavier oligomers) were obtained for different olefins, and effective C-C coupling was observed between isobutene and isopentene. Among the substrates investigated, facile oligomerization occurred very specifically for the structures with an α-double bond and two substituents at the second carbon atom of the main carbon chain. The possible oligomerization mechanism of light olefins was discussed based on the reactivity and selectivity trends. Moreover, the deactivation and regeneration of S-MOF-808 were investigated. The catalyst deactivates via two mechanisms which predominance depends on the substrate and reaction conditions. Above 110 °C, a loss of acidic sites was observed due to water desorption, and the deactivated catalyst could be regenerated by a simple treatment with water vapor. For C5 substrates and unsaturated ethers, the oligomers with increased molecular weight caused deactivation via blocking of the active sites, which could not be readily reversed. These findings offer the first systematic report on carbocation-mediated olefin coupling within MOFs in which the Brønsted acidity is associated with the secondary building units of the MOF itself and is not related to any guest substance hosted within its pore system.

Identification of the strong Brønsted acid site in a metal-organic framework solid acid catalyst.

It remains difficult to understand the surface of solid acid catalysts at the molecular level, despite their importance for industrial catalytic applications. A sulfated zirconium-based metal-organic framework, MOF-808-SO4, was previously shown to be a strong solid Brønsted acid material. In this report, we probe the origin of its acidity through an array of spectroscopic, crystallographic and computational characterization techniques. The strongest Brønsted acid site is shown to consist of a specific arrangement of adsorbed water and sulfate moieties on the zirconium clusters. When a water molecule adsorbs to one zirconium atom, it participates in a hydrogen bond with a sulfate moiety that is chelated to a neighbouring zirconium atom; this motif, in turn, results in the presence of a strongly acidic proton. On dehydration, the material loses its acidity. The hydrated sulfated MOF exhibits a good catalytic performance for the dimerization of isobutene (2-methyl-1-propene), and achieves a 100% selectivity for C8 products with a good conversion efficiency.

Bioinspired Metal-Organic Framework Catalysts for Selective Methane Oxidation to Methanol.

Particulate methane monooxygenase (pMMO) is an enzyme that oxidizes methane to methanol with high activity and selectivity. Limited success has been achieved in incorporating biologically relevant ligands for the formation of such active site in a synthetic system. Here, we report the design and synthesis of metal-organic framework (MOF) catalysts inspired by pMMO for selective methane oxidation to methanol. By judicious selection of a framework with appropriate topology and chemical functionality, MOF-808 was used to postsynthetically install ligands bearing imidazole units for subsequent metalation with Cu(I) in the presence of dioxygen. The catalysts show high selectivity for methane oxidation to methanol under isothermal conditions at 150 °C. Combined spectroscopies and density functional theory calculations suggest bis(µ-oxo) dicopper species as probable active site of the catalysts.

Structure of Copper-Cobalt Surface Alloys in Equilibrium with Carbon Monoxide Gas.

We studied the structure of the copper-cobalt (CuCo) surface alloy, formed by Co deposition on Cu(110), in dynamic equilibrium with CO. Using scanning tunneling microscopy (STM), we found that, in vacuum at room temperature and at low Co coverage, clusters of a few Co atoms substituting Cu atoms form at the surface. At CO pressures in the Torr range, we found that up to 2.5 CO molecules can bind on a single Co atom, in carbonyl-like configurations. Based on high-resolution STM images, together with density functional theory calculations, we determined the most stable CuCo cluster structures formed with bound CO. Such carbonyl-like formation manifests in shifts in the binding energy of the Co core-level peaks in X-ray photoelectron spectra, as well as shifts in the vibrational modes of adsorbed CO in infrared reflection absorption spectra. The multiple CO adsorption on a Co site weakens the Co-CO bond and thus reduces the C-O bond scission probability. Our results may explain the different product distribution, including higher selectivity toward alcohol formation, when bimetallic CuCo catalysts are used compared to pure Co.

The effect of aluminum and platinum additives on hydrogen adsorption on mesoporous silicates.

Recent theoretical predictions indicate that functional groups and additives could have a favorable impact on the hydrogen adsorption characteristics of sorbents; however, no definite evidence has been obtained to date and little is known about the impact of such modifications on the thermodynamics of hydrogen uptake and overall capacity. In this work, we investigate the effect of two types of additives on the cryoadsorption of hydrogen to mesoporous silica. First, Lewis and Brønsted acid sites were evaluated by grafting aluminum to the surface of mesoporous silica (MCF-17) and characterizing the resulting silicate materials' surface area and the concentration of Brønsted and Lewis acid sites created. Heat of adsorption measurements found little influence of surface acidity on the enthalpy of hydrogen cryoadsorption. Secondly, platinum nanoparticles of 1.5 nm and 7.1 nm in diameter were loaded into MCF-17, and characterized by TEM. Hydrogen absorption measurements revealed that the addition of small amounts of metallic platinum nanoparticles increases by up to two-fold the amount of hydrogen adsorbed at liquid nitrogen temperature. Moreover, we found a direct correlation between the size of platinum particles and the amount of hydrogen stored, in favor of smaller particles.

Supported Au Nanoparticles with N-Heterocyclic Carbene Ligands as Active and Stable Heterogeneous Catalysts for Lactonization.

Attachment of N-heterocyclic carbenes (NHCs) on the surface of metal nanoparticle (NP) catalysts permits fine-tuning of catalytic activity and product selectivity. Yet, NHC-coated Au NPs have been seldom used in catalysis beyond hydrogenation chemistry. One challenge in this field has been to develop a platform that permits arbitrary ligand modification without having to compromise NP stability toward aggregation or leaching. Herein, we exploit the strategy of supported dendrimer-encapsulated metal clusters (DEMCs) to achieve aggregation-stable yet active heterogeneous Au NP catalysts with NHC ligands. Dendrimers function as aggregation-inhibitors during the NP synthesis, and NHCs, well-known for their strong attachment to the gold surface, provide a handle to modify the stereochemistry, stereoelectronics, and chemical functionality of the NP surface. Indeed, compared to "ligandless" Au NPs which are virtually inactive below 80 °C, the NHC-ligated Au NP catalysts enable a model lactonization reaction to proceed at 20 °C on the same time scale (hours). Based on Eyring analysis, proto-deauration is the turnover-limiting step accelerated by the NHC ligands. Furthermore, the use of chiral NHCs led to asymmetric induction (up to 16% enantiomeric excess) in the lactonization transformations, which demonstrates the potential of supported DEMCs with ancillary ligands in enantioselective catalysis.

Fluoroethylene Carbonate Induces Ordered Electrolyte Interface on Silicon and Sapphire Surfaces as Revealed by Sum Frequency Generation Vibrational Spectroscopy and X-ray Reflectivity.

The cyclability of silicon anodes in lithium ion batteries (LIBs) is affected by the reduction of the electrolyte on the anode surface to produce a coating layer termed the solid electrolyte interphase (SEI). One of the key steps for a major improvement of LIBs is unraveling the SEI's structure-related diffusion properties as charge and discharge rates of LIBs are diffusion-limited. To this end, we have combined two surface sensitive techniques, sum frequency generation (SFG) vibrational spectroscopy, and X-ray reflectivity (XRR), to explore the first monolayer and to probe the first several layers of electrolyte, respectively, for solutions consisting of 1 M lithium perchlorate (LiClO4) salt dissolved in ethylene carbonate (EC) or fluoroethylene carbonate (FEC) and their mixtures (EC/FEC 7:3 and 1:1 wt %) on silicon and sapphire surfaces. Our results suggest that the addition of FEC to EC solution causes the first monolayer to rearrange itself more perpendicular to the anode surface, while subsequent layers are less affected and tend to maintain their, on average, surface-parallel arrangements. This fundamental understanding of the near-surface orientation of the electrolyte molecules can aid operational strategies for designing high-performance LIBs.

Surface Structures of Model Metal Catalysts in Reactant Gases.

Atomic scale knowledge of the surface structure of a metal catalyst is essential for fundamentally understanding the catalytic reactions performed on it. A correlation between the true atomic surface structure of a metal catalyst under reaction conditions and the corresponding catalytic performance is the key in pursuing mechanistic insight at a molecular level. Here the surface structures of model, metal catalysts in both ultrahigh vacuum (UHV) and gaseous environments of CO at a wide range of pressures are discussed. The complexity of observed surface structures in CO is illustrated, driving the necessity for visualization of the catalytic metals under realistic reaction conditions. Technical barriers for visualization of metal surfaces in situ at high temperature and high pressure are discussed.