Dynamic Copper Site Redispersion through Atom Trapping in Zeolite Defects.

Single-site copper-based catalysts have shown remarkable activity and selectivity for a variety of reactions. However, deactivation by sintering in high-temperature reducing environments remains a challenge and often limits their use due to irreversible structural changes to the catalyst. Here, we report zeolite-based copper catalysts in which copper oxide agglomerates formed after reaction can be repeatedly redispersed back to single sites using an oxidative treatment in air at 550 °C. Under different environments, single-site copper in Cu-Zn-Y/deAlBeta undergoes dynamic changes in structure and oxidation state that can be tuned to promote the formation of key active sites while minimizing deactivation through Cu sintering. For example, single-site Cu2+ reduces to Cu1+ after catalyst pretreatment (270 °C, 101 kPa H2) and further to Cu0 nanoparticles under reaction conditions (270-350 °C, 7 kPa EtOH, 94 kPa H2) or accelerated aging (400-450 °C, 101 kPa H2). After regeneration at 550 °C in air, agglomerated CuO was dispersed back to single sites in the presence and absence of Zn and Y, which was verified by imaging, in situ spectroscopy, and catalytic rate measurements. Ab initio molecular dynamics simulations show that solvation of CuO monomers by water facilitates their transport through the zeolite pore, and condensation of the CuO monomer with a fully protonated silanol nest entraps copper and reforms the single-site structure. The capability of silanol nests to trap and stabilize copper single sites under oxidizing conditions could extend the use of single-site copper catalysts to a wider variety of reactions and allows for a simple regeneration strategy for copper single-site catalysts.

Multivariate Bayesian Optimization of CoO Nanoparticles for CO2 Hydrogenation Catalysis.

The hydrogenation of CO2 holds promise for transforming the production of renewable fuels and chemicals. However, the challenge lies in developing robust and selective catalysts for this process. Transition metal oxide catalysts, particularly cobalt oxide, have shown potential for CO2 hydrogenation, with performance heavily reliant on crystal phase and morphology. Achieving precise control over these catalyst attributes through colloidal nanoparticle synthesis could pave the way for catalyst and process advancement. Yet, navigating the complexities of colloidal nanoparticle syntheses, governed by numerous input variables, poses a significant challenge in systematically controlling resultant catalyst features. We present a multivariate Bayesian optimization, coupled with a data-driven classifier, to map the synthetic design space for colloidal CoO nanoparticles and simultaneously optimize them for multiple catalytically relevant features within a target crystalline phase. The optimized experimental conditions yielded small, phase-pure rock salt CoO nanoparticles of uniform size and shape. These optimized nanoparticles were then supported on SiO2 and assessed for thermocatalytic CO2 hydrogenation against larger, polydisperse CoO nanoparticles on SiO2 and a conventionally prepared catalyst. The optimized CoO/SiO2 catalyst consistently exhibited higher activity and CH4 selectivity (ca. 98%) across various pretreatment reduction temperatures as compared to the other catalysts. This remarkable performance was attributed to particle stability and consistent H* surface coverage, even after undergoing the highest temperature reduction, achieving a more stable catalytic species that resists sintering and carbon occlusion.

An Exceptionally Mild and Scalable Solution-Phase Synthesis of Molybdenum Carbide Nanoparticles for Thermocatalytic CO2 Hydrogenation.

Transition metal carbides (TMCs) have demonstrated outstanding potential for utilization in a wide range of catalytic applications because of their inherent multifunctionality and tunable composition. However, the harsh conditions required to prepare these materials have limited the scope of synthetic control over their physical properties. The development of low-temperature, carburization-free routes to prepare TMCs would unlock the versatility of this class of materials, enhance our understanding of their physical properties, and enable their cost-effective production at industrial scales. Here, we report an exceptionally mild and scalable solution-phase synthesis route to phase-pure molybdenum carbide (α-MoC1-x) nanoparticles (NPs) in a continuous flow millifluidic reactor. We exploit the thermolytic decomposition of Mo(CO)6 in the presence of a surface-stabilizing ligand and a high boiling point solvent to yield MoC1-x NPs that are colloidally stable and resistant to bulk oxidation in air. To demonstrate the utility of this synthetic route to prepare catalytically active TMC NPs, we evaluated the thermochemical CO2 hydrogenation performance of α-MoC1-x NPs dispersed on an inert carbon support. The α-MoC1-x/C catalyst exhibited a 2-fold increase in both activity on a per-site basis and selectivity to C2+ products as compared to the bulk α-MoC1-x analogue.

Activating Molybdenum Carbide Nanoparticle Catalysts under Mild Conditions Using Thermally Labile Ligands.

Transition-metal carbides are promising low-cost materials for various catalytic transformations due to their multifunctionality and noble-metal-like behavior. Nanostructuring transition-metal carbides offers advantages resulting from the large surface-area-to-volume ratios inherent in colloidal nanoparticle catalysts; however, a barrier for their utilization is removal of the long-chain aliphatic ligands on their surface to access active sites. Annealing procedures to remove these ligands require temperatures greater than the catalyst synthesis and catalytic reaction temperatures and may further result in coking or particle sintering that can reduce catalytic performance. One way to circumvent this problem is by replacing the long-chain aliphatic ligands with smaller ligands that can be easily removed through low-temperature thermolytic decomposition. Here, we present the exchange of native oleylamine ligands on colloidal α-MoC1-x nanoparticles for thermally labile tert-butylamine ligands. Analyses of the ligand exchange reaction by solution 1H NMR spectroscopy, FT-IR spectroscopy, and thermogravimetric analysis-mass spectrometry (TGA-MS) confirm the displacement of 60% of the native oleylamine ligands for the thermally labile tert-butylamine, which can be removed with a mild activation step at 250 °C. Catalytic site densities were determined by carbon monoxide (CO) chemisorption, demonstrating that the mild thermal treatment at 250 °C activates ca. 25% of the total binding sites, while the native oleylamine-terminated MoC1-x nanoparticles showed no available surface binding sites after this low-temperature treatment. The mild pretreatment at 250 °C also shows distinctly different initial activities and postinduction period selectivities in the CO2 hydrogenation reaction for the ligand exchanged MoC1-x nanoparticle catalysts and the as-prepared material.

Performing In Situ Closed-Cell Gas Reactions in the Transmission Electron Microscope.

Gas reactions studied by in situ electron microscopy can be used to capture the real-time morphological and microchemical transformations of materials at length scales down to the atomic level. In situ closed-cell gas reaction (CCGR) studies performed using (scanning) transmission electron microscopy (STEM) can separate and identify localized dynamic reactions, which are extremely challenging to capture using other characterization techniques. For these experiments, we used a CCGR holder that utilizes microelectromechanical systems (MEMS)-based heating microchips (hereafter referred to as "E-chips"). The experimental protocol described here details the method for performing in situ gas reactions in dry and wet gases in an aberration-corrected STEM. This method finds relevance in many different materials systems, such as catalysis and high-temperature oxidation of structural materials at atmospheric pressure and in the presence of various gases with or without water vapor. Here, several sample preparation methods are described for various material form factors. During the reaction, mass spectra obtained with a residual gas analyzer (RGA) system with and without water vapor further validates gas exposure conditions during reactions. Integrating an RGA with an in situ CCGR-STEM system can, therefore, provide critical insight to correlate gas composition with the dynamic surface evolution of materials during reactions. In situ/operando studies using this approach allow for detailed investigation of the fundamental reaction mechanisms and kinetics that occur at specific environmental conditions (time, temperature, gas, pressure), in real-time, and at high spatial resolution.

Electrocatalytic CO2 Reduction over Cu3P Nanoparticles Generated via a Molecular Precursor Route.

The design of nanoparticles (NPs) with tailored morphologies and finely tuned electronic and physical properties has become a key strategy for controlling selectivity and improving conversion efficiency in a variety of important electrocatalytic transformations. Transition metal phosphide NPs, in particular, have emerged as a versatile class of catalytic materials due to their multifunctional active sites and composition- and phase-dependent properties. Access to targeted transition metal phosphide NPs with controlled features is necessary to tune the catalytic activity. To this end, we have established a solution-synthesis route utilizing a molecular precursor containing M-P bonds to generate solid metal phosphide NPs with controlled stoichiometry and morphology. We expand here the application of molecular precursors in metal phosphide NP synthesis to include the preparation of phase-pure Cu3P NPs from the thermal decomposition of [Cu(H)(PPh3)]6. The mechanism of [Cu(H)(PPh3)]6 decomposition and subsequent formation of Cu3P was investigated through modification of the reaction parameters. Identification and optimization of the critical reaction parameters (i.e., time, temperature, and oleylamine concentration) enabled the synthesis of phase-pure 9-11 nm Cu3P NPs. To probe the multifunctionality of this materials system, Cu3P NPs were investigated as an electrocatalyst for CO2 reduction. At low overpotential (-0.30 V versus RHE) in 0.1 M KHCO3 electrolyte, Cu3P-modified carbon paper electrodes produced formate (HCOO-) at a maximum Faradaic efficiency of 8%.

Dehydrogenative Coupling of Methanol for the Gas-Phase, One-Step Synthesis of Dimethoxymethane over Supported Copper Catalysts.

Oxymethylene dimethyl ethers (OMEs), CH3-(OCH2)n-OCH3, n = 1-5, possess attractive low-soot diesel fuel properties. Methanol is a key precursor in the production of OMEs, providing an opportunity to incorporate renewable carbon sources via gasification and methanol synthesis. The costly production of anhydrous formaldehyde in the typical process limits this option. In contrast, the direct production of OMEs via a dehydrogenative coupling (DHC) reaction, where formaldehyde is produced and consumed in a single reactor, may address this limitation. We report the gas-phase DHC reaction of methanol to dimethoxymethane (DMM), the simplest OME, with n = 1, over bifunctional metal-acid catalysts based on Cu. A Cu-zirconia-alumina (Cu/ZrAlO) catalyst achieved 40% of the DMM equilibrium-limited yield under remarkably mild conditions (200 °C, 1.7 atm). The performance of the Cu/ZrAlO catalyst was attributed to metallic Cu nanoparticles that enable dehydrogenation and a distribution of acid strengths on the ZrAlO support, which reduced the selectivity to dimethyl ether compared to a that obtained with a Cu/Al2O3 catalyst. The DMM formation rate of 6.1 h-1 compares favorably against well-studied oxidative DHC approaches over non-noble, mixed-metal oxide catalysts. The results reported here set the foundation for further development of the DHC route to OME production, rather than oxidative approaches.

Application of phase-pure nickel phosphide nanoparticles as cathode catalysts for hydrogen production in microbial electrolysis cells.

Transition metal phosphide catalysts such as nickel phosphide (Ni2P) have shown excellent activities for the hydrogen evolution reaction, but they have primarily been studied in strongly acidic or alkaline electrolytes. In microbial electrolysis cells (MECs), however, the electrolyte is usually a neutral pH to support the bacteria. Carbon-supported phase-pure Ni2P nanoparticle catalysts (Ni2P/C) were synthesized using solution-phase methods and their performance was compared to Pt/C and Ni/C catalysts in MECs. The Ni2P/C produced a similar quantity of hydrogen over a 24 h cycle (0.29 ±â€¯0.04 L-H2/L-reactor) as that obtained using Pt/C (0.32 ±â€¯0.03 L-H2/L) or Ni/C (0.29 ±â€¯0.02 L-H2/L). The mass normalized current density of the Ni2P/C was 14 times higher than that of the Ni/C, and the Ni2P/C exhibited stable performance over 11 days. Ni2P/C may therefore be a useful alternative to Pt/C or other Ni-based catalysts in MECs due to its chemical stability over time.

Localized Pd overgrowth on cubic Pt nanocrystals for enhanced electrocatalytic oxidation of formic acid.

Binary Pt/Pd nanoparticles were synthesized by localized overgrowth of Pd on cubic Pt seeds for the investigation of electrocatalytic formic acid oxidation. The binary particles exhibited much less self-poisoning and a lower activation energy relative to Pt nanocubes, consistent with the single crystal study.

Highly selective synthesis of catalytically active monodisperse rhodium nanocubes.

Monodisperse sub-10 nm Rh nanocubes were synthesized with high selectivity (>85%) by a seedless polyol method. The {100} faces of the Rh NCs were effectively stabilized by chemically adsorbed Br- ions from trimethyl(tetradecyl)ammonium bromide (TTAB). This simple one-step polyol route can be readily applied to the preparation of Pt and Pd nanocubes. Moreover, the organic molecules of PVP and TTAB that encapsulated the Rh nanocubes did not prevent catalytic activity for pyrrole hydrogenation and CO oxidation.

Probing the interaction of poly(vinylpyrrolidone) with platinum nanocrystals by UV-Raman and FTIR.

The vibrational spectra of platinum nanoparticles (2.4-9 nm) capped with poly(N-vinylpyrrolidone) (PVP) were investigated by deep UV-Raman and FTIR spectroscopy and compared with those of pure PVP. Raman spectra of PVP/Pt show selective enhancement of C=O, C-N, and CH2 vibrational modes attributed to the pyrrolidone ring. Selective enhancement of ring vibrations is attributed both to the resonance Raman effect and SERS chemical enhancement. A red shift of the PVP carbonyl frequency on the order of 60 cm-1 indicates the formation of strong >C=O-Pt bonds. It is concluded that PVP adheres to the nanoparticles through a charge-transfer interaction between the pyrrolidone rings and surface Pt atoms. Heating the Pt nanoparticles under reducing conditions initiates the decomposition of the capping agent, PVP, at a temperature 100 degrees C below that of pure PVP. Under oxidizing conditions, both PVP/Pt and PVP degrade to form amorphous carbon.

Surface Chemistry Exchange of Alloyed Germanium Nanocrystals: A Pathway Toward Conductive Group IV Nanocrystal Films.

We present an expansion of the mixed-valence iodide reduction method for the synthesis of Ge nanocrystals (NCs) to incorporate low levels (∼1 mol %) of groups III, IV, and V elements to yield main-group element-alloyed Ge NCs (Ge1-xEx NCs). Nearly every main-group element (E) that surrounds Ge on the periodic table (Al, P, Ga, As, In, Sn, and Sb) may be incorporated into Ge1-xEx NCs with remarkably high E incorporation into the product (>45% of E added to the reaction). Importantly, surface chemistry modification via ligand exchange allowed conductive films of Ge1-xEx NCs to be prepared, which exhibit conductivities over large distances (25 µm) relevant to optoelectronic device development of group IV NC thin films.

Nanocrystal bilayer for tandem catalysis.

Supported catalysts are widely used in industry and can be optimized by tuning the composition and interface of the metal nanoparticles and oxide supports. Rational design of metal-metal oxide interfaces in nanostructured catalysts is critical to achieve better reaction activities and selectivities. We introduce here a new class of nanocrystal tandem catalysts that have multiple metal-metal oxide interfaces for the catalysis of sequential reactions. We utilized a nanocrystal bilayer structure formed by assembling platinum and cerium oxide nanocube monolayers of less than 10 nm on a silica substrate. The two distinct metal-metal oxide interfaces, CeO(2)-Pt and Pt-SiO(2), can be used to catalyse two distinct sequential reactions. The CeO(2)-Pt interface catalysed methanol decomposition to produce CO and H(2), which were subsequently used for ethylene hydroformylation catalysed by the nearby Pt-SiO(2) interface. Consequently, propanal was produced selectively from methanol and ethylene on the nanocrystal bilayer tandem catalyst. This new concept of nanocrystal tandem catalysis represents a powerful approach towards designing high-performance, multifunctional nanostructured catalysts.

In situ spectroscopic detection of SMSI effect in a Ni/CeO2 system: hydrogen-induced burial and dig out of metallic nickel.

In situ APPES technique demonstrates that the strong metal support interaction effect (SMSI) in the Ni-ceria system is associated with the decoration and burial of metallic particles by the partially reduced support, a phenomenon reversible by evacuation at high temperature of the previously absorbed hydrogen.

Probing compositional variation within hybrid nanostructures.

We present a detailed analysis of the structural and magnetic properties of solution-grown PtCo-CdS hybrid structures in comparison to similar free-standing PtCo alloy nanoparticles. X-ray absorption spectroscopy is utilized as a sensitive probe for identifying subtle differences in the structure of the hybrid materials. We found that the growth of bimetallic tips on a CdS nanorod substrate leads to a more complex nanoparticle structure composed of a PtCo alloy core and thin CoO shell. The core-shell architecture is an unexpected consequence of the different nanoparticle growth mechanism on the nanorod tip, as compared to free growth in solution. Magnetic measurements indicate that the PtCo-CdS hybrid structures are superparamagnetic despite the presence of a CoO shell. The use of X-ray spectroscopic techniques to detect minute differences in atomic structure and bonding in complex nanosystems makes it possible to better understand and predict catalytic or magnetic properties for nanoscale bimetallic hybrid materials.