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Chen, Linxiao

Publications and source records attributed to Chen, Linxiao.

At least 19 records
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DOE OSTI2024

Insights into Dopant-Mediated Tuning of Silica-Supported Mo Metal Centers for Enhanced Olefin Metathesis

Here, we show that the electronic environment around active Mo centers supported on mesoporous silicates can be tuned by the addition of transition metals creating highly dispersed bimetallic catalysts that display enhanced activity for ethylene + 2-butene metathesis to propylene. The bimetallic catalysts are prepared by incorporating electrophilic Lewis acid metals (M) such as Nb, Ta, Zr, or Hf as dopant promoters into mesoporous KIT-6 supports using a one-pot sol–gel technique followed by impregnation of the Mo species. All the bimetallic Mo/M-KIT-6 catalysts display better activity than monometallic Mo/KIT-6 catalyst (28.7 ± 1.1 mmol (mol Mo s ) –1 ), with (Mo/Nb-KIT-6) catalysts exhibiting maximum propylene formation rates (54.2 ± 0.5 mmol (mol Mo s ) –1 ) at an identical Mo loading.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydrogen Spillover Is Regulating Minority Rh 1 Active Sites on TiO 2 in Room-Temperature Ethylene Hydrogenation

The complicated dynamics of active sites on single-atom catalysts under reducing conditions limits their applications in hydrogenation reactions and mechanistic understanding. Herein, we report that on Rh 1 /TiO 2 , *H spillover during room-temperature ethylene hydrogenation hydroxylates and reduces TiO 2 , enhancing the intrinsic activity of Rh 1 by 9-fold. Spectroscopic and kinetic evidence suggests that the spillover of *H is suppressed by their facile reaction with C 2 H 4 , most of the spilled *H are nonreactive spectators, and >99% turnovers occur on a small subset (<20%) of exposed “active Rh 1 ”. Steady-state kinetics indicates competitive adsorption between H and C 2 H 4 , H 2 dissociation is the rate-determining step, and the apparent activation barrier (E a,app ) of the reaction is ~48 kJ/mol. The evolution of Rh 1 under H 2 was further tracked by spectroscopic and microscopic techniques at elevated temperatures. At 200 °C, more Rh 1 are exposed, but these Rh 1 are at least 5-fold less active than that of the “active Rh 1 ”. At 300 °C, Rh clusters derived from Rh 1 become the main active sites, shifting E a,app to 62 kJ/mol, characteristic of Rh nanoparticles. At ≥400 °C, larger and more active Rh particles in the strong metal–support interaction state are created. In conclusion, this work revealed the unexpected regulation effects of *H spillover on M 1 active sites under ambient conditions, differentiated the minority active M 1 sites, and demonstrated how the stability of M 1 under reducing atmospheres affects hydrogenation catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Ultrasmall Pd Clusters in FER Zeolite Alleviate CO Poisoning for Effective Low-Temperature Carbon Monoxide Oxidation

Ultra small Pd 4 clusters form in the micropores of FER zeolite during low temperature treatment (100 °C) in the presence of humid CO gas. They effectively catalyze CO oxidation below 100°C, whereas Pd nanoparticles are not active as they are poisoned by CO. Using catalytic measurements, infrared (IR) spectroscopy, X-ray absorption spectroscopy (EXAFS), microscopy, and density functional theory calculations we provide the molecular level insight into this previously unreported phenomenon. Pd nanoparticles get covered with CO at low temperatures which effectively blocks O 2 activation until CO desorption occurs. Small Pd clusters in zeolites, in contrast, demonstrate fluxional behavior in the presence of CO, which significantly increases their affinity for binding O 2 . In conclusion, our study shows a pathway for achieving low temperature CO oxidation activity on the basis of well-defined Pd/zeolite system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Efficient and selective dual-pathway polyolefin hydro-conversion over unexpectedly bifunctional M/TiO 2 -anatase catalysts

The huge scale of plastic waste generation and its environmental consequences drive the demands for catalytic plastic upcycling processes. Here, we report efficient polypropylene (PP) hydro-conversion over Ru and Ni supported on a sol-gel anatase TiO 2 (TiO 2 -A-SG). A small number of Brønsted acid sites on TiO 2 -A-SG enables hydrocracking, improving efficiency, steering the selectivity towards high-valued C 4-20 , and allowing more isomerization, compared to Ru-based monofunctional hydrogenolysis catalysts. The relative contribution of hydrocracking increases with lower hydrogen partial pressure, more branched substrates, and lower Ru loading. Ni/TiO 2 -A-SG exhibits superior hydrocracking activity and selectivity to Ni on conventional Brønsted-acidic supports, particularly zeolites. Further, mechanistic studies shows fast isomerization and sequential ß-scissions caused by strong polymer-catalyst interaction and fast cracking with abundant 3 C. This favors C 4-12 formation and prevents secondary reactions. This work demonstrated a novel, highly efficient noble-metal-free catalyst for plastic waste upcycling, while advancing the mechanistic understanding of polyolefin hydro-conversion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Dynamic Evolution of Palladium Single Atoms on Anatase Titania Support Determines the Reverse Water–Gas Shift Activity

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/TiO 2 -anatase SAC (Pd 1 /TiO 2 ) 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 TiO 2 by H 2 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. The activation by H 2 is accompanied by the partial sintering of single Pd atoms (Pd 1 ) into disordered, flat, ~1 nm diameter clusters (Pd n ). The highly active Pd sites in the new coordination environment under H 2 are eliminated by oxidation, which, when performed at high temperature, also re-disperses Pd n and facilitates the reduction of TiO 2 . In contrast, Pd 1 sinters into crystalline, ~5 nm particles (Pd NP ) during CO treatment, deactivating Pd 1 /TiO 2 . During the rWGS reaction, the two Pd evolution pathways co-exist. The activation by H 2 dominates, leading to the increasing rate with time-on-stream, and steady-state Pd active sites similar with the ones formed under H 2 . 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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Single Ru(II) Ions on Ceria as a Highly Active Catalyst for Abatement of NO

Atom trapping leads to catalysts with atomically dispersed Ru 1 O 5 sites on (100) facets of ceria, as identified by spectroscopy and DFT calculations. This is a new class of ceria-based materials with Ru properties drastically different from the known M/ceria materials. They show excellent activity in catalytic NO oxidation, a critical step that requires use of large loadings of expensive noble metals in diesel aftertreatment systems. Ru 1 /CeO 2 is stable during continuous cycling, ramping, and cooling as well as the presence of moisture. Furthermore, Ru 1 /CeO 2 shows very high NO x storage properties due to formation of stable Ru–NO complexes as well as a high spill-over rate of NO x onto CeO 2 . Only ~0.05 wt % of Ru is required for excellent NO x storage. Ru 1 O 5 sites exhibit much higher stability during calcination in air/steam up to 750 °C in contrast to RuO 2 nanoparticles. Here we clarify the location of Ru(II) ions on the ceria surface and experimentally identify the mechanism of NO storage and oxidation using DFT calculations and in situ DRIFTS/mass spectroscopy. Moreover, we show excellent reactivity of Ru 1 /CeO 2 for NO reduction by CO at low temperatures: only 0.1–0.5 wt % of Ru is sufficient to achieve high activity. Modulation-excitation in situ infrared and XPS measurements reveal the individual elementary steps of NO reduction by CO on an atomically dispersed Ru ceria catalyst, highlighting unique properties of Ru 1 /CeO 2 and its propensity to form oxygen vacancies/Ce +3 sites that are critical for NO reduction, even at low Ru loadings. Our study highlights the applicability of novel ceria-based single-atom catalysts to NO and CO abatement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Disordered, Sub-Nanometer Ru Structures on CeO 2 are Highly Efficient and Selective Catalysts in Polymer Upcycling by Hydrogenolysis

We report non-degradable polyolefin plastics pose severe environmental threats, and thus demand efficient upcycling technologies. In this work, we discovered that low-loading (= 0.25 wt%) Ru/CeO 2 exhibits remarkable catalytic performance in the hydrogenolysis of polypropylene (PP), polyethylene (PE), and n-C 16 H 34 that is superior to high-loading (= 0.5 wt%) Ru/CeO 2 . They possess high PP conversion efficiency (7-fold increase over current literature reports), low selectivity towards undesired CH 4 , and good isomerization ability. In the low-loading range, the intrinsic activity of Ru in PP hydrogenolysis increases as the particle size decreases, opposite of the trend in the high-loading range. Detailed characterization revealed that the abrupt changes in catalytic behaviors coincide with Ru species transitioning from well-defined to highly disordered structures in the low-loading domain. The disordered Ru species were shown to be sub-nanometer in size and cationic. Mechanistically, the regioselectivity and the rate dependence on hydrogen pressure of C-C bond cleavage are different on low- and high-loading Ru/CeO 2 , both explained by the higher coverage of adsorbed hydrogen (*H) on low-loading Ru/CeO 2 . This work uncovers the remarkable catalytic performance of highly disordered, sub-nanometer, cationic Ru species in polyolefin hydrogenolysis, opening immense opportunities to develop effective, selective, and versatile catalysts for plastic upcycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Temperature-Dependent Communication between Pt/Al 2 O 3 Catalysts and Anatase TiO 2 Dilutant: the Effects of Metal Migration and Carbon Transfer on the Reverse Water–Gas Shift Reaction

In heterogeneous catalysis, unexpected effects from the supposedly inert reactor dilutant are not rare, but related understanding is lacking and inconsistent. Here we report investigations of the impacts of the anatase TiO 2 dilutant on the reverse water-gas shift (rWGS) reaction over Pt/Al 2 O 3 catalysts. Combining detailed kinetic data with microscopic and spectroscopic results, we demonstrate that the catalyst-dilutant communication depends on temperature. At high temperature (400 °C), Pt migrate from Al 2 O 3 to TiO 2 , resulting in higher dispersion and activity, without changing reaction mechanisms. The Pt migration is general to catalysts of different Pt nuclearity and various oxide dilutants. In contrast, at low temperature (250 °C), carboxylic acids (in particular acetic acid) present in the ambient air and adsorbed on TiO 2 are transferred onto Al 2 O 3 in close contact, effectively blocking the formate rWGS pathway. As a result, the rWGS can only proceed through the carboxyl pathway, and hence is significantly slower. The acetate transfer affects catalysts of different Pt nuclearity and support, but is unique to anatase TiO 2 dilutant. As the acetate layer is slowly removed under H 2 or the rWGS stream, the activity recovers. This work elucidates the complicated communication between catalysts and dilutants, which has general implications in heterogeneous catalysis, and resolves inconsistency in related reports in the literature. Finally, the impacts that anatase TiO 2 dilution has on the rWGS also unveil mechanistic understanding that further confirms the two co-existing rWGS pathways.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Tuning Ligand–Coordinated Single Metal Atoms on TiO 2 and their Dynamic Response during Hydrogenation Catalysis

Ligand-coordinated supported catalysts (LCSCs) are of growing interest for heterogeneous single-atom catalysis. Here, the effect of the choice of organic ligand on the activity and stability of TiO 2 -supported single-atom Pt-ligand catalysts was investigated for ethylene hydrogenation. The activity of these catalysts showed a significant dependence on the choice of ligand and also correlated with coordination number for Pt-ligand and Pt-Cl - . Of the three ligands examined in this study, the one with the lowest Pt coordination number, 1,10-phenanthroline-5,6-dione (PDO), showed the lowest reaction temperature and highest reaction rate, likely due to those metal sites being more accessible to reactant adsorption. In-situ X-ray absorption spectroscopy (XAS) experiments showed that the activity also correlated with good heterolytic dissociation of hydrogen, which was supported by OH/OD exchange experiments and was the rate-determining step of the hydrogenation reaction. In these in-situ XAS experiments up to 190 degrees C, the supported Pt-ligand catalyst showed excellent stability against structural and chemical change. Instead of Pt, the PDO ligand could be coordinated with Ir on TiO 2 to form Ir LCSCs that showed slow activation by loss of Ir-Cl bonds, then excellent stability in the hydrogenation of ethylene. Furthermore, these results provide the chance to engineer ligand-coordinated supported catalysts at the single-atom catalyst level by the choice of ligand and enable new applications at relatively high temperature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Ligand-coordinated Ir single-atom catalysts stabilized on oxide supports for ethylene hydrogenation and their evolution under a reductive atmosphere

In this work, we present a novel series of oxide-supported Ir-ligand single-atom catalysts (SACs) for ethylene hydrogenation. The SACs were created by a metal–ligand self-assembly strategy developed by our group, using one of two ligands, either 1,10-phenanthroline-5,6-dione (PDO) or 3,6-Di-2-pyridyl-1,2,4,5-tetrazine (DPTZ), on powder supports of either CeO 2 or MgO. Characterization by XAS, XPS, and CO adsorption proved that Ir exist principally as highly uniform, cationic single-atoms. Ir SACs show significantly higher durability and metal utilization efficiency than Ir nanoparticle (NP) catalysts during ethylene hydrogenation at 100 °C, as well as excellent stability, as no Ir aggregates were detected after >10 h reaction. The activity can be tuned by ligand and support effects: PDO and CeO 2 are superior to DPTZ and MgO, respectively. This tunability is attributed to differences in H 2 activation capability, which results from differences in support reducibility, electron density on Ir, and, potentially, the local coordination environment of Ir. The Ir SACs lose H 2 activation activity either under inert gas or under H 2 . Through XPS and in situ XAS studies, we attributed the former to the reversible loss of Ir hydride, which is the active species for H 2 activation, and the latter to irreversible over-hydrogenation and loss of Ir–O/N coordination. This work presents a new type of Ir hydrogenation SACs that are more durable, efficient, and tunable than supported Ir NPs, while more stable than homogeneous Ir complexes. It also offers fundamental understanding regarding ligand and support effects, as well as the evolution of Ir single-atoms under H 2 , instructing future design of stable, effective hydrogenation SACs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

X-ray photoelectron spectroscopy data from lightly Pd doped TiO 2 anatase nanoparticles

Here, two sets of XPS spectra from ≈13 nm slightly Pd-doped anatase TiO 2 particles are reported. Anatase is the most stable form of TiO 2 for small particles, and these spectra are the first spectra from nano-sized anatase to appear in Surface Science Spectra. The high resolution Ti 2p spectrum has an extended range showing important loss features not appearing in most of the earlier data records. The O 1s spectrum also has loss features often ignored, and in this case, the loss features are overlapped by some of the Ti 2s peak features that complicate quantitative analysis. The spectra reported here were used as example spectra in a guide to backgrounds in XPS, and the availability of these spectra in digital form allows LRH-analysts to compare their background selections and analysis approach to those discussed in the guide.

36 MATERIALS SCIENCE↗
DOE OSTI2020

In Situ Dispersion of Palladium on TiO 2 During Reverse Water–Gas Shift Reaction: Formation of Atomically Dispersed Palladium

The application of single-atom catalysts (SACs) to high-temperature hydrogenation requires materials that thermodynamically favor metal atom isolation over cluster formation. Here, we show that Pd can be predominantly dispersed as isolated atoms onto TiO 2 during the reverse water-gas shift (rWGS) reaction at 400 °C. Achieving atomic dispersion requires an artificial increase of the absolute TiO 2 surface area by an order of magnitude and can be accomplished by physically mixing a precatalyst (Pd/TiO 2 ) with neat TiO 2 prior to the rWGS reaction. Furthermore, the in situ dispersion of Pd was reflected through a continuous increase of rWGS activity over 92 h and supported by kinetic analysis, infrared and X-ray absorption spectroscopies and scanning transmission electron microscopy. The thermodynamic stability of Pd under high-temperature rWGS conditions is associated with Pd-Ti coordination, which manifests upon O-vacancy formation and the artificial increase in TiO 2 surface area.

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