46 Search Results

Artificial intelligence (AI) is increasingly integrated into catalysis science, enabling agentic workflows in which AI systems perceive inputs, reason under constraints, plan, and autonomously execute in silico or physical experiments with minimal human intervention. While these closed-loop capabilities hold promise for accelerating catalysis research, they introduce new sources of variability that can undermine rigor and reproducibility (R&R). These risks are particularly pronounced in heterogeneous catalysis, where subtleties in catalyst synthesis, activation, and testing can strongly influence catalytic outcomes. To address these challenges, we introduce TRACE-AI (transparent reporting for agentic catalysis enabled by artificial intelligence) as a set of community guidelinesmore » with a publication checklist. TRACE-AI emphasizes end-to-end traceability of catalysis campaigns, linking scientific queries to data and models, reasoning and actions, and the knowledge acquired. Here, by promoting standardized reporting, TRACE-AI aims to cultivate a foundation for accelerating scientific discovery while reinforcing R&R as autonomous catalysis laboratories continue to emerge.« less

C−H bond functionalization of arenes with boranes continues to be a challenge in catalysis, with late transition and rare earth metals shown to be catalytically active. In this study, group 4 metallocenes grafted onto acidic sulfated zirconia (SZO) are demonstrated to catalyze arene borylation with pinacolborane (HBpin). Catalysis studies at partial HBpin conversions (59−68%) using Cp₂M(Me)/SZO (M = Ti, Zr, or Hf; Cp = cyclopentadienyl) catalysts reveal that Zr exhibits greater selectivity and activity than Ti and Hf. At 0.16 mol % of Zr, Cp₂ZrMe/SZO achieves 332 turnovers at high HBpin conversion (86%), making this catalyst comparably active to previouslymore » reported Ir and Rh C−H borylation catalysts. At 160 °C, a maximum chemoselectivity of 82% for PhBpin was observed at 24% HBpin conversion. The superior activity of ionic Cp₂ZrMe/SZO compared to neutral Cp₂ZrMe/SiO₂ demonstrates the borylation mechanism relies on the highly electrophilic, coordinatively unsaturated cationic sites stabilized by the weakly coordinating sulfated support. Furthermore, both catalysts significantly outperform their molecular analogues, Cp₂ZrMe₂ and [Cp₂ZrMe][B(C₆F₅)₄], suggesting that the support enhances catalytic performance by stabilizing the active species.« less

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO₂ regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO₂ from simulated flue gas (10% v/v CO₂ in N₂) with electroreduction of NH₄HCO₃ to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO₂ capture with C/N ratio of 0.65 was achieved using 2.5 M NH₃ from simulated flue gas. Electrolysis of the resulting NH₄HCO₃ on the Ni- SACmore » delivered an 85% CO Faradaic efficiency at 100 mA/cm² with excellent tolerance to NH₃/NH₄⁺ as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.« less

Safe and efficient hydrogen storage is pivotal for enabling a clean hydrogen economy. Liquid organic hydrogen carriers (LOHCs) offer a practical solution, but their deployment is hindered by the lack of highly active and economical dehydrogenation catalysts. Here, we report a metal-free catalyst design that overcomes the long-standing trade-off between crystallinity and surface area in two-dimensional frameworks for highly efficient dehydrogenation of LOHCs. A flux-assisted reconstruction strategy transforms amorphous borocarbonitrides (AM-BCN) into highly crystalline, defect-rich BCN nanosheets (C-BCN) with large surface area and accessible porosity, as confirmed by complementary spectroscopic, x-ray, and neutron analyses. C-BCN catalyzes the acceptor-less dehydrogenation ofmore » aza-fused LOHCs with quantitative hydrogen release under mild conditions, outperforming AM-BCN and previously reported metal-free scaffolds. Mechanistic insights from x-ray, neutron scattering, and theoretical calculations identify open C-B-N and N-B-N defect motifs as the primary active sites. This work establishes a generalizable strategy to engineer crystalline, porous, defect-rich two-dimensional lattices and demonstrates a highly active metal-free platform for LOHC dehydrogenation with high-purity H2 generation.« less

The photoactivity of three porphyrin-based metal-organic frameworks (PMOFs) incorporating Al, Ga, and In nodes was systematically evaluated using the photooxidation of an organic sulfide (2-chloroethyl ethyl sulfide, or CEES; a mustard gas simulant). Faster photodegradation of CEES was observed for PMOFs with heavier metal nodes, placing In-PMOF as the most efficient photocatalyst in the series. Guided by this insight, we developed CSLA-10, a MOF integrating In nodes and Sn-doped porphyrin linker to synergistically amplify heavy-atom effects at both the nodes and ligand levels. CSLA-10 exhibited the fastest reported CEES photooxidation to date, achieving a half-life of 38 s in methanolmore » under blue LED irradiation. When grafted onto textiles, CSLA-10 enabled solvent-free CEES degradation in air/O₂ with a half-life of 2.7 min and complete conversion within 7 min, representing the most rapid full degradation reported under solvent-free conditions. Furthermore, this work establishes a dual heavy-atom strategy for enhancing intersystem crossing and singlet oxygen generation in porphyrin MOFs, providing a rational design principle for next-generation photocatalysts for the degradation of toxic organic sulfides.« less

Artificial intelligence (AI) is poised to transform heterogeneous catalysis, opening avenues for catalytic materials discovery. By uncovering intricate patterns in high-dimensional data, AI has been reshaping our pursuit of sustainable catalytic processes across the energy, environmental and chemical sectors. This promise, however, hinges on overcoming fundamental barriers, including limitations in data availability and quality, challenges in the generalizability and interpretability of data-augmented decisions, and the persistent gap between in silico predictions and experiments. Furthermore, we outline a forward-looking roadmap for deeply integrating AI into heterogeneous catalysis with an AI-ready data ecosystem, multimodal foundation models, and ultimately autonomous laboratories to acceleratemore » the development of next-generation catalytic technologies via AI-empowered human–machine collaboration.« less

Metal-free heteroatom-doped carbocatalysts are promising alternatives to precious metals for alkane direct dehydrogenation/hydrogenation and reversible hydrogen storage, yet the nature of their active sites remains poorly understood. This study investigates a nitrogen assembly carbocatalyst (NAC) for efficient and selective hydrocarbon dehydrogenation. For ethylbenzene, NAC maintains a selectivity of >99% towards styrene at a conversion of >20% for 120 hours at a weight hourly space velocity of 0.4 h⁻¹. Theoretical studies suggest that closely spaced graphitic nitrogen sites are the active sites for the chemisorption and dehydrogenation of ethylbenzene, and the robustness of these sites is supported by ambient-pressure X-ray photoelectronmore » spectroscopy. Kinetic analysis reveals a temperature-dependent reaction profile, with distinct activation energies and reaction orders at 300 and 500 °C. Isotope-labeling studies indicate that dehydrogenation primarily proceeds via initial cleavage of the benzylic C–H bond, and the faster desorption of ethylbenzene at higher temperatures contributes to the difference in kinetic behavior. Importantly, the NAC catalyst also enables efficient hydrogenation of styrene back to ethylbenzene at 250 °C, allowing for reversible hydrogen storage using a single catalyst at moderate temperatures. These findings underscore the significance of constructing high densities of closely spaced graphitic nitrogen in carbocatalysts for enhanced activity and selectivity.« less

The industrial implementation of electrosynthesis for chemical manufacturing remains constrained by the limited surface area of conventional electrodes. Herein, this challenge is addressed by designing a carbon nanofiber@carbon felt (CNF@CF) electrode platform that combines the high conductivity, flexibility, and ease of handling of commercial carbon felts (CF) with the large surface area and tunable surface chemistry of carbon nanofibers (CNFs). CNFs are deliberately grown onto the CF scaffold to form a sword-in-sheath structure, where entangled nanofibers wrap the felt macrofibers to provide excellent mechanical stability and electrical conductivity without binders. CNF@CF is evaluated both as an electrode and as amore » catalyst support for the electrochemical hydrogenation of cis,cis-muconic acid (ccMA), a biobased platform molecule key to the production of performance polyamides and renewable Nylon 6,6. As a noncatalytic electrode for the partial hydrogenation to trans-3-hexenedioic acid, CNF@CF achieves a threefold increase in both cumulative productivity and Faradaic efficiency (FE) compared to bare CF. A similar boost in catalytic activity and energy efficiency is observed using Pd/CNF@CF for the hydrogenation of ccMA to adipic acid. These results highlight the opportunities of the CNF@CF platform for electro-organic synthesis and sustainable chemical manufacturing.« less

As a complex composite of cellulose, hemicellulose, and lignin, plant lignocellulose has long served as a major resource for biomass conversion, materials engineering, and bio-based product development. High-resolution structural insights enabled by solid-state nuclear magnetic resonance (ssNMR) now allow the mapping of polymer interfaces, identification of functional group accessibility, and tracking of molecular organization during processing, all of which are critical factors for optimizing catalytic strategies. These insights could drive transformative progress in lignocellulose-based applications, including selective depolymerization, improved pretreatment design, and efficient upcycling of lignin into resins, plastics, and biomedical materials. In industry-relevant contexts, such as biofuel generation andmore » renewable material manufacturing, understanding the hydration dynamics, cross-linking patterns, and structural heterogeneity is also essential. The ability to visualize these features in native biomass presents a unique opportunity to develop new strategies for sustainability and performance. As the structural toolbox continues to expand, it is becoming a central enabler for innovations in renewable energy, green chemistry, and advanced bioproducts.« less

Advancing efficient hydrogen storage technologies is essential for enabling a sustainable energy future, especially in onboard applications. While hydrogen offers high gravimetric energy density and zero-emission combustion, its low volumetric energy density presents significant storage challenges. Metal-organic frameworks (MOFs), well known for their tunable porosity and high surface areas, have emerged as promising candidates for adsorption-based hydrogen storage. This study investigated a chemically robust zirconium-based MOF, MOF-808, as a representative platform for hydrogen storage enhancement through metal ion doping. Various divalent metal ions were introduced into MOF-808 via one-pot synthesis or post-synthetic modification (PSM) to evaluate their effects on metalmore » doping efficiency, framework stability, and hydrogen adsorption performance. Our findings demonstrate that metal doping enhanced the hydrogen binding affinity of MOF-808 while preserving its structural integrity and excellent stability. A Mg-doped MOF, MOF-808@Mg 2:1, showed a 59% increase in hydrogen uptake, and a Cu-doped MOF, MOF-808-ZrCu, exhibited a 33% increase in isosteric heat of adsorption for H₂ compared to the pristine MOF-808 activated at the same temperature. This work highlights the potential of metal-functionalized stable MOFs for practical hydrogen storage applications. Furthermore, these materials are also being studied for their potential to enhance CO₂ adsorption.« less