Propane wet reforming over PtSn nanoparticles on γ-Al2O3 for acetone synthesis.

Acetone serves as an important solvent and building block for the chemical industry, but the current industrial synthesis of acetone is generally accompanied by the energy-intensive and costly cumene process used for phenol production. Here we propose a sustainable route for acetone synthesis via propane wet reforming at a moderate temperature of 350 oC with the use of platinum-tin nanoparticles supported on γ-aluminium oxide (PtSn/γ-Al2O3) as catalyst. We achieve an acetone productivity of 858.4 µmol/g with a selectivity of 57.8% among all carbon-based products and 99.3% among all liquid products. Detailed spectroscopic and controlled experiments reveal that the acetone is formed through a tandem catalytic process involving propene and isopropanol as intermediates. We also demonstrate facile ketone synthesis via wet reforming with the use of different alkanes (e.g., n-butane, n-pentane, n-hexane, n-heptane, and n-octane) as substrates, proving the wide applicability of this strategy.

Facet-Dependent Diversity of Pt-O Coordination for Pt1/CeO2 Catalysts Achieved by Oriented Atomic Deposition.

The surface chemistry of CeO2 is dictated by the well-defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt-O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt-O3 coordination on the predominantly exposed {111} facets, while the photo-deposition method achieves oriented atomic deposition for Pt-O4 coordination into the "nano-pocket" structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low-temperature activity for CO oxidation, the photo-deposited Pt1/CeO2 exhibits uncustomary strong metal-support interaction and extraordinary high-temperature stability. The preparation methods dictate the facet-dependent diversity of Pt-O coordination, resulting in the further activity-selectivity trade-off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano-catalysts.

Facet sensitivity of iron carbides in Fischer-Tropsch synthesis.

Fischer-Tropsch synthesis (FTS) is a structure-sensitive reaction of which performance is strongly related to the active phase, particle size, and exposed facets. Compared with the full-pledged investigation on the active phase and particle size, the facet effect has been limited to theoretical studies or single-crystal surfaces, lacking experimental reports of practical catalysts, especially for Fe-based catalysts. Herein, we demonstrate the facet sensitivity of iron carbides in FTS. As the prerequisite, {202} and {112} facets of χ-Fe5C2 are fabricated as the outer shell through the conformal reconstruction of Fe3O4 nanocubes and octahedra, as the inner cores, respectively. During FTS, the activity and stability are highly sensitive to the exposed facet of iron carbides, whereas the facet sensitivity is not prominent for the chain growth. According to mechanistic studies, {202} χ-Fe5C2 surfaces follow hydrogen-assisted CO dissociation which lowers the activation energy compared with the direct CO dissociation over {112} surfaces, affording the high FTS activity.

Close Intimacy between PtIn Clusters and Zeolite Channels for Ultrastability toward Propane Dehydrogenation.

Propane dehydrogenation (PDH) serves as a pivotal intentional technique to produce propylene. The stability of PDH catalysts is generally restricted by the readsorption of propylene which can subsequently undergo side reactions for coke formation. Herein, we demonstrate an ultrastable PDH catalyst by encapsulating PtIn clusters within silicalite-1 which serves as an efficient promoter for olefin desorption. The mean lifetime of PtIn@S-1 (S-1, silicalite-1) was calculated as 37317 h with high propylene selectivity of >97% at 580 °C with a weight hourly space velocity (WHSV) of 4.7 h-1. With an ultrahigh WHSV of 1128 h-1, which pushed the catalyst away from the equilibrium conversion to 13.3%, PtIn@S-1 substantially outperformed other reported PDH catalysts in terms of mean lifetime (32058 h), reaction rates (3.42 molpropylene gcat-1 h-1 and 341.90 molpropylene gPt-1 h-1), and total turnover number (14387.30 kgpropylene gcat-1). The developed catalyst is likely to lead the way to scalable PDH applications.

The Importance of Sintering-Induced Grain Boundaries in Copper Catalysis to Improve Carbon-Carbon Coupling.

Syngas conversion serves as a gas-to-liquid technology to produce liquid fuels and valuable chemicals from coal, natural gas, or biomass. During syngas conversion, sintering is known to deactivate the catalyst owing to the loss of active surface area. However, the growth of nanoparticles might induce the formation of new active sites such as grain boundaries (GBs) which perform differently from the original nanoparticles. Herein, we reported a unique Cu-based catalyst, Cu nanoparticles with in situ generated GBs confined in zeolite Y (denoted as activated Cu/Y), which exhibited a high selectivity for C5+ hydrocarbons (65.3 C%) during syngas conversion. Such high selectivity for long-chain products distinguished activated Cu/Y from typical copper-based catalysts which mainly catalyze methanol synthesis. This unique performance was attributed to the GBs, while the zeolite assisted the stabilization through spatial confinement. Specifically, the GBs enabled H-assisted dissociation of CO and subsequent hydrogenation into CHx*. CHx* species not only serve as the initiator but also directly polymerize on Cu GBs, known as the carbide mechanism. Meanwhile, the synergy of GBs and their vicinal low-index facets led to the CO insertion where non-dissociative adsorbed CO on low-index facets migrated to GBs and inserted into the metal-alkyl bond for the chain growth.

Electrocatalytic Reforming of Polylactic Acid Plastic Hydrolysate over Dynamically Formed γ-NiOOH.

Upcycling plastic waste into valuable commodity chemicals with clean energy is an appealing strategy for mitigating environmental issues. Polylactic acid (PLA), a biodegradable plastic that is produced annually in millions of tons, can be chemically recycled to valuable products instead of being degraded to carbon dioxide. Here, we demonstrate an electrochemical reforming of PLA hydrolysate to acetate and acetonate using nickel phosphide nanosheets on nickel foam (Ni2P/NF) as the catalyst. The Ni2P/NF catalyst was synthesized by electrochemical deposition and phosphide treatment and showed excellent catalytic activity and ∼100% Faraday efficiency for electroreforming PLA to acetate and acetonate in an H-cell. Moreover, a stable performance of more than 90% Faraday efficiency for value-added organics was achieved for a duration of 100 h in a flow cell at a current density of 100 mA cm-2 and a potential below 1.5 V vs. RHE. In situ characterization revealed that the catalyst underwent electrochemical reforming during the reaction to produce γ-phase NiOOH with high electrochemical activity. This work introduces a new and green solution for the treatment of waste PLA, presenting a low-cost and highly efficient strategy for electrically reforming plastics.

Exploring the Strain Effect in Single Particle Electrochemistry using Pd Nanocrystals.

Tuning the surface strain of heterogeneous catalysts is recognized as a powerful strategy for tailoring their catalytic activity. However, a clear understanding of the strain effect in electrocatalysis at single-particle resolution is still lacking. Here, we explore the electrochemical hydrogen evolution reaction (HER) of single Pd octahedra and icosahedra with the same surface bounded {111} crystal facet and similar sizes using scanning electrochemical cell microscopy (SECCM). It is revealed that tensilely strained Pd icosahedra display significantly superior HER electrocatalytic activity. The estimated turnover frequency at -0.87 V vs RHE on Pd icosahedra is about two times higher than that on Pd octahedra. Our single-particle electrochemistry study using SECCM at Pd nanocrystals unambiguously highlights the importance of tensile strain on electrocatalytic activity and may offer new strategy for understanding the fundamental relationship between surface strain and reactivity.

Constructing imine groups on the surface of Cu1/Pd(111) as a novel strategy for CO2 hydrogenation to methanol.

Developing a promising strategy to improve the limited selectivity and activity of traditional Pd-Cu bimetallic catalysts for CO2 hydrogenation to methanol (CH3OH) remains a grand challenge. By using density functional theory calculations, we discovered that introducing imine groups on the Cu1/Pd(111) surface through a condensation reaction of aldehydes and amines is an intriguing approach for simultaneously enhancing the selectivity and activity of Cu1/Pd(111) for CO2 hydrogenation to CH3OH. The imine groups formed by amino reactions with acrolein on the Cu1/Pd(111) surface (C3H4O@NH2-Cu1/Pd(111)) improved the turnover frequency (TOF). The imine group optimized the electronic structure of active sites and increased electron transfer to the anti-bonding orbital of CO2, facilitating the activity of C3H4O@NH2-Cu1/Pd(111) for CO2 hydrogenation to CH3OH. Besides, the inhibition of CO by-products and the low desorption energy of CH3OH were responsible for the high selectivity of C3H4O@NH2-Cu1/Pd(111) for CH3OH. This work advances our understanding of the role of imines in catalysis and provides a new strategy for designing excellent functional group-modified catalysts for the hydrogenation of CO2 to CH3OH.

Selective CO2 electrolysis to CO using isolated antimony alloyed copper.

Renewable electricity-powered CO evolution from CO2 emissions is a promising first step in the sustainable production of commodity chemicals, but performing electrochemical CO2 reduction economically at scale is challenging since only noble metals, for example, gold and silver, have shown high performance for CO2-to-CO. Cu is a potential catalyst to achieve CO2 reduction to CO at the industrial scale, but the C-C coupling process on Cu significantly depletes CO* intermediates, thus limiting the CO evolution rate and producing many hydrocarbon and oxygenate mixtures. Herein, we tune the CO selectivity of Cu by alloying a second metal Sb into Cu, and report an antimony-copper single-atom alloy catalyst (Sb1Cu) of isolated Sb-Cu interfaces that catalyzes the efficient conversion of CO2-to-CO with a Faradaic efficiency over 95%. The partial current density reaches 452 mA cm-2 with approximately 91% CO Faradaic efficiency, and negligible C2+ products are observed. In situ spectroscopic measurements and theoretical simulations reason that the atomic Sb-Cu interface in Cu promotes CO2 adsorption/activation and weakens the binding strength of CO*, which ends up with enhanced CO selectivity and production rates.

Selectively anchoring single atoms on specific sites of supports for improved oxygen evolution.

The homogeneity of single-atom catalysts is only to the first-order approximation when all isolated metal centers interact identically with the support. Since the realistic support with various topologies or defects offers diverse coordination environments, realizing real homogeneity requires precise control over the anchoring sites. In this work, we selectively anchor Ir single atoms onto the three-fold hollow sites (Ir1/TO-CoOOH) and oxygen vacancies (Ir1/VO-CoOOH) on defective CoOOH surface to investigate how the anchoring sites modulate catalytic performance. The oxygen evolution activities of Ir1/TO-CoOOH and Ir1/VO-CoOOH are improved relative to CoOOH through different mechanisms. For Ir1/TO-CoOOH, the strong electronic interaction between single-atom Ir and the support modifies the electronic structure of the active center for stronger electronic affinity to intermediates. For Ir1/VO-CoOOH, a hydrogen bonding is formed between the coordinated oxygen of single-atom Ir center and the oxygenated intermediates, which stabilizes the intermediates and lowers the energy barrier of the rate-determining step.

Persistent Luminescence Nanoplatform with Fenton-like Catalytic Activity for Tumor Multimodal Imaging and Photoenhanced Combination Therapy.

Reactive oxygen species-mediated tumor chemodynamic therapy and photodynamic therapy have captured extensive attention in practical cancer combination therapies. However, the severe treatment conditions and the hypoxic microenvironment of solid tumors significantly limit the efficacy of these therapies. This work demonstrates the design and fabrication of a multifunctional persistent luminescence nanoplatform (PHFI, refers to PLNP-HSA-Fe3+-IR780) for cancer multimodal imaging and effective photoenhanced combination therapy. The near-infrared-emitted persistent luminescence nanoparticles (PLNP) was modified with human serum albumin (HSA) combined with an IR780 probe and Fe3+. The synthesized PHFI possesses high longitudinal relaxivity, obvious photoacoustic contrast signals, and long-lasting persistent luminescence, indicating that PHFI can be used for cancer magnetic resonance imaging, photoacoustic imaging, and persistent luminescence multimodal imaging. PHFI shows intrinsic photoenhanced Fenton-like catalytic activities as well as photodynamic and photothermal effects and thereby can effectively overcome severe treatment conditions for killing tumor cells. It is worth noting that PHFI serving as a rechargeable internal light source for photoenhanced combination therapy was first disclosed. We believe that our work shows the great potential of PHFI for cancer theranostics and will advance the development of PLNP-based nanoplatforms in tumor catalytic therapy.