66 Search Results

Catalysis informatics has received tremendous attention in recent years as a tool to design catalysts and discover unique descriptors that capture the relationships between chemical properties and catalytic performance. One of the stop-gaps in understanding catalytic effects, which is often ignored and limits the deployment of data science tools, relates to the lack of uniform data. The catalytic cleavage of C–X (X= H, C, N, and O) bonds is relevant to many fundamental catalytic processes. In this Perspective, we performed data analytics on four groups of C–X cleavage reactions that are common in production, upcycling, or reactive separation: the C–Cmore » cleavage in cyclopropyl alcohol, the C–H cleavage in hydroacylation reactions, the C–O cleavage in β-O-4 linkages, and the C–N cleavage in amides, using experimental data collected from the literature to understand their underlying correlations. Experimental variables of high impact are identified for each reaction by dimensionality reduction methods. We highlight the urgent need for experimental data sets that include full details on the reaction conditions, such as reagent concentration, reaction temperature, or time in machine-readable forms. We discuss the potential improvement of the data of these reactions and promising approaches such as autonomous experiments to fill the gaps in unbiased experimental data. Finally, we also address the early stage consideration of separation aspects in the experimental design of efficient catalytic systems for these fundamental examples of chemical reactivity.« less

As nations unite to curb anthropogenic greenhouse gas emissions, the decarbonization of the chemical industry has been propelled to the forefront of scientific research. Renewable electricity will play a central role in this effort. In addition to powering chemical plants and allowing for the sustainable production of heat to drive thermocatalytic processes, renewable electricity also provides the chemical industry with opportunities to engage in the sustainability revolution and broadly reduce its environmental footprint through breakthrough innovations in direct electrochemical transformations. The electrification of chemical synthesis—electrosynthesis—is a promising route to promote sustainability without compromising economic competitiveness. Electrosynthesis uses electrons both asmore » an energy source to drive reactions and as a green reagent for chemical reductions and oxidations under ambient conditions. Therefore, it holds tremendous potential (pun intended) to increase selectivity to desired products, open green reaction pathways for challenging transformations (e.g., Birch reduction, epoxidations, coupling reactions), and reduce chemical waste.« less

Although crown ethers can selectively bind many metal cations, little is known regarding the solution properties of crown ether complexes of the uranyl dication, UO₂²⁺. Here, in this work, the synthesis and characterization of isolable complexes in which the uranyl dication is bound in an 18-crown-6-like moiety are reported. A tailored macrocyclic ligand, templated with a Pt(II) center, captures UO₂²⁺ in the crown moiety, as demonstrated by results from single-crystal X-ray diffraction analysis. The U(V) oxidation state becomes accessible at a quite positive potential (E_1/2) of –0.18 V vs Fc^+/0 upon complexation, representing the most positive U^VI/U^V potential yet reportedmore » for the UO₂ⁿ⁺ core. Isolation and characterization of the U(V) form of the crown complex are also reported here; there are no prior reports of reduced uranyl crown ether complexes, but U(V) is clearly stabilized by crown chelation. Joint computational studies show that the electronic structure of the U(V) form results in significant weakening of U–O_oxo bonding despite the quite positive reduction potential at which this species can be accessed, underscoring that crown-ligated uranyl species could demonstrate unique reactivity under only modestly reducing conditions.« less

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 throughmore » 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. Importantly, 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.« less

Proton transfer is critically important to many electrocatalytic reactions, and directed proton delivery could open new avenues for the design of electrocatalysts. However, although this approach has been successful in molecular electrocatalysis, proton transfer has not received the same attention in heterogeneous electrocatalyst design. Here, in this work, we report that a metal oxide proton relay can be built within heterogeneous electrocatalyst architectures and improves the kinetics of electrochemical hydrogen evolution and oxidation reactions. The volcano-type relationship between activity enhancement and pK_a of amine additives confirms this improvement; we observe maximum rate enhancement when the pK_a of a proton relaymore » matches the pH of the electrolyte solution. Density-functional-theory-based reactivity studies reveal a decreased proton transfer energy barrier with a metal oxide proton relay. These findings demonstrate the possibility of controlling the proton delivery and enhancing the reaction kinetics by tuning the chemical properties and structures at heterogeneous interfaces.« less

Abstract Efficient direct air capture (DAC) of CO ₂ will require strategies to deal with the relatively low concentration in the atmosphere. One such strategy is to employ the combination of a CO ₂ ‐selective membrane coupled with a CO ₂ capture solvent acting as a draw solution. Here, the interactions between a leading water‐lean carbon‐capture solvent, a polyether ether ketone (PEEK)‐ionene membrane, CO ₂ , and combinations were probed using advanced NMR techniques coupled with advanced simulations. We identify the speciation and dynamics of the solvent, membrane, and CO ₂ , presenting spectroscopic evidence of CO ₂ diffusion throughmore » benzylic regions within the PEEK‐ionene membrane, not spaces in the ionic lattice as expected. Our results demonstrate that water‐lean capture solvents provide a thermodynamic and kinetic funnel to draw CO ₂ from the air through the membrane and into the bulk solvent, thus enhancing the performance of the membrane. The reaction between the carbon‐capture solvent and CO ₂ produces carbamic acid, disrupting interactions between the imidazolium (Im ⁺ ) cations and the bistriflimide anions within the PEEK‐ionene membrane, thereby creating structural changes through which CO ₂ can diffuse more readily. Consequently, this restructuring results in CO ₂ diffusion at the interface that is faster than CO ₂ diffusion in the bulk carbon‐capture solvent.« less

Boron-based catalysts have been shown to be both active and selective for driving the oxidative dehydrogenation of propane (ODHP) without the use of precious metals. This reaction occurs at temperatures that melt the oxide catalyst which challenges our ability to identify the liquid structures of the boron oxide phase under reaction conditions, hindering the understanding of its active sites and reaction mechanism. By combining ab initio molecular dynamics simulation, in-situ Raman characterization, and microkinetic modeling, we propose that the di-coordinated boron sites (BO2) in liquid boron oxide are the active species for O2 activation under reaction conditions. The formed peroxy-likemore » species (>B-O-O-B<) can be viewed as a moderate oxidant for ODHP. The dynamical >B-O* dangling bond originated from >B-O-O-B< site as well as the liquid B2O3 structure itself, plays a critical role in the abstraction of H atoms from propane (C3H7 radical formation). Microkinetic modeling reveals C3H7 radical formation to be the main rate controlling step (~75% degree of rate control) with the dehydration of boron hydroxyls (B-OHs) to recover the di-coordinated boron active sites controlling the remainder of the rate (~25% degree of rate control). Moreover, the activation barriers are found to strongly depend upon the surface B-OH concentration. These findings provide significant insights into the active site and reaction mechanisms on boron-based catalysts for ODHP and underlie the importance of understanding the liquid nature of the catalyst to account for the catalytic activity.« less

Research interest in single-atom catalysts (SACs) has been continuously rising. However, the lack of understanding of the dynamic behaviors of SACs during applications hinder catalyst development and mechanistic understanding. Herein, we report on the evolution of active sites over Pd/TiO₂-anatase SAC (Pd₁/TiO₂) in the reverse water-gas shift (rWGS) reaction. Combining kinetics, in-situ characterization, and theory, we show that at T ≥ 350 °C, the reduction of TiO₂ by H₂ alters the coordination environment of Pd, creating Pd sites with partially cleaved Pd-O interfacial bonds and a unique electronic structure that exhibit high intrinsic rWGS activity through the carboxyl pathway. Themore » activation by H₂ is accompanied by the partial sintering of single Pd atoms (Pd₁) into disordered, flat, ~1 nm diameter clusters (Pd_n). The highly active Pd sites in the new coordination environment under H₂ are eliminated by oxidation, which, when performed at high temperature, also re-disperses Pd_n and facilitates the reduction of TiO₂. In contrast, Pd₁ sinters into crystalline, ~5 nm particles (Pd_NP) during CO treatment, deactivating Pd₁/TiO₂. During the rWGS reaction, the two Pd evolution pathways co-exist. The activation by H₂ dominates, leading to the increasing rate with time-on-stream, and steady-state Pd active sites similar with the ones formed under H₂. Finally, this work demonstrates how the coordination environment and nuclearity of metal sites on a SAC evolve during catalysis and pre-treatments, and how their activity is modulated by these behaviors. These insights on SAC dynamics and structure-function relationship are valuable to mechanistic understanding and catalyst design.« less