Measuring Long-Range 13C–13C Correlations on a Surface under Natural Abundance Using Dynamic Nuclear Polarization-Enhanced Solid-State Nuclear Magnetic Resonance

We report that spatial (\u3c1 \u3enm) proximity between different molecules in solid bulk materials and, for the first time, different moieties on the surface of a catalyst, can be established without isotope enrichment by means of homonuclear CHHC solid-state nuclear magnetic resonance experiment. This 13C–13C correlation measurement, which hitherto was not possible for natural-abundance solids, was enabled by the use of dynamic nuclear polarization. Importantly, it allows the study of long-range correlations in a variety of materials with high resolution

High Throughput Screening of 3D Printable Resins: Adjusting the Surface and Catalytic Properties of Multifunctional Architectures

Identification of 3D printable materials is crucial to expand the breadth of physical and chemical properties attainable by additive manufacturing. Stereolithography (SLA), a widespread 3D printing method based on resin photo-polymerization, is ideally suited for exploring a large variety of monomers to produce functional three-dimensional solids of diverse properties. However, for most of the commercially available SLA 3D printers, screening monomers and resin compositions requires large volumes (~150 mL) in each printing cycle, making the process costly and inefficient. Herein, a high throughput block (HTB) adaptor was developed to screen arrays of monomers and resin compositions, consuming lower volumes (\u3c 2 mL) and less time per print (\u3c 1/16 based on a 44 matrix) than using the original hardware. Using this approach, a library of materials with different surface hydrophobicities were 3D printed by including long chain acrylates in the resins. In addition, several metal salts were dissolved in an acrylic acid-based resin, 3D printed and screened as heterogeneous catalysts for the selective aerobic oxidation of benzyl alcohol to benzaldehyde. Cu(II)-based resins produced the most active structures. Combinations of Cu(II) and long chain acrylate monomers were then used to 3D print complex catalytic architectures with varying degrees of hydrophobicity. Linear relationships were observed between 3D printed surface area, surface hydrophobicity and catalyst performance. For a high surface Schwarz P topology ca. 60 % enhancement in the catalytic activity of Cu(II) was attained by replacing the parent resin with one containing hydrophobic isodecyl groups, indicating that the immediate environment of the catalytic site affected its performance. The HTB enables fast screening of resins for 3D printing multifunctional architectures with intrinsic catalytic activity, tunable surface properties, and minimal waste

Substrate–Support Interactions Mediate Hydrogenation of Phenolic Compounds by Pd/CeO2 Nanorods

Ceria-supported palladium (Pd/CeO2) has spawned significant attention in recent years due to its ability to catalyze selective hydrogenation of phenolic compounds to cyclohexanones and cyclohexanols at a mild temperature and pressure. However, the mechanistic basis by which ceria enhances catalytic conversion is still unclear. Here, we use the increase in the 13C transverse relaxation rate upon the addition of nanoparticles (NPs) (13C ΔR2) to investigate the adsorption of phenolic compounds on the surface of the Pd/CeO2 catalyst by solution NMR. We show that hydroxyphenols adsorb on the support more efficiently than underivatized phenol and methoxyphenols and that phenol derivatives with an oxygen atom at position 2 (i.e., 2-hydroxyphenol and 2-methoxyphenol) form very stable interactions with the Pd site of Pd/CeO2. An analysis of the kinetics of hydrogenation revealed that catalytic conversion is linearly correlated with the ability of the substrate to form interactions with the CeO2 support and is inhibited by the formation of stable substrate–Pd adducts. Our data suggest that CeO2–substrate interactions mediate phenol hydrogenation more efficiently than Pd–substrate interactions and explain the exceptional catalytic performance reported for Pd/CeO2

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

The stability of palladium supported on ceria (Pd/CeO2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. A deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is propose

Direct 3D Printing of Catalytically Active Structures

3D printing of materials with active functional groups can provide customdesigned structures that promote chemical conversions. Herein, catalytically active architectures were produced by photopolymerizing bifunctional molecules using a commercial stereolithographic 3D printer. Functionalities in the monomers included a polymerizable vinyl group to assemble the 3D structures and a secondary group to provide them with active sites. The 3D-printed architectures containing accessible carboxylic acid, amine, and copper carboxylate functionalities were catalytically active for the Mannich, aldol, and Huisgen cycloaddition reactions, respectively. The functional groups in the 3D-printed structures were also amenable to post-printing chemical modification. As proof of principle, chemically active cuvette adaptors were 3D printed and used to measure in situ the kinetics of a heterogeneously catalyzed Mannich reaction in a conventional solution spectrophotometer. In addition, 3D-printed millifluidic devices with catalytically active copper carboxylate complexes were used to promote azidealkyne cycloaddition under flow conditions. The importance of controlling the 3D architecture of the millifluidic devices was evidenced by enhancing reaction conversion upon increasing the complexity of the 3D prints