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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.
Electrical, thermal, and H 2 O and CO 2 poisoning behaviors of PrNi 0.5 Co 0.5 O 3-δ electrode for intermediate temperature protonic ceramic electrochemical cells
PrNi 0.5 Co 0.5 O 3-δ (PNC) exhibits adequate total electrical conductivity (~300 S/cm at 400–600 °C) and moisture has no significant effect on it. The thermal expansion coefficient of PNC is 17.6 × 10 –6 /K by dilatometry and 18.43 × 10 –6 /K by in situ XRD. PNC also demonstrates chemical stability against H 2 O and CO 2 . However, PNC symmetrical cell over proton-conducting BaZr 0.4 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ (BZCYYb4411) electrolyte shows significant H 2 O and CO 2 poisoning when those are introduced into O 2 –N 2 mixture. In comparison, symmetrical cells with PNC electrode over the oxygen ion conducting Ce 0.9 Gd 0.1 O 2-δ (GDC) electrolyte show no H 2 O and CO 2 poisoning under similar conditions. Here, it is hypothesized that poisoning from H 2 O and CO 2 of the PNC proton conducting symmetrical cell is caused by their adsorption on the BZCYYb4411 electrolyte instead of PNC electrode. Such a hypothesis is supported by the H 2 O and CO 2 adsorption behaviors on PNC and BZCYYb4411 powder surfaces, as measured by temperature programmed desorption (TPD).
Sharp-tip enhanced catalytic CO oxidation by atomically dispersed Pt 1 /Pt 2 on a raised graphene oxide platform
Revealing structure–activity relationships of graphene-supported atomically dispersed transition metal catalysts is of key importance in catalysis chemistry and materials science. In this work, we report a first-principles theoretical study on O 2 activation and CO oxidation catalyzed by atomically dispersed Pt 1 /Pt 2 anchored on a raised graphene (Gr) platform. The unique sharp-tip structure of the protuberant graphene platform (carbon-tip) can collect extra polarization electrons on the Pt-tip, promoting electron transfer between the catalyst and adsorbates, and greatly enhancing the chemical activity. Higher carbon-tips on defective graphene oxide with a carbon vacancy (Gr-V) produce more polarization electrons, a more localized electric field, and a larger up-shift of the d-orbital center of the Pt-tip, resulting in better catalytic performance. The carbon-tip enhancement reduces the energy barrier for the CO oxidation on Pt 1 O 2 /Gr-V from 1.19 eV to 0.56 eV compared with Pt 1 on planar Gr. In addition, CO poisoning is significantly alleviated, with the CO poisoning rate Γ θ reduced from 2.00 eV to 0.52 eV. Moreover, a linear relationship between the activation barrier and the binding energy of adsorbates is found for various atomically dispersed Pt-tip catalysts on the raised graphene oxide platform. Importantly, the order of catalytic activity is consistent with the carbon-tip enhancement, i.e., Pt 1 O 2 /Gr-V > Pt 2 O 4 /Gr-V > Pt 1 O 2 /Gr > Pt 2 O 4 /Gr. These findings provide important guidance for rational design of atomically dispersed catalysts.
Hydrogen activation by rhodium under the cover of a copper oxide thin film
Here, the activation of reactants by catalytically active metal sites at metal-oxide interfaces is important for understanding the effect of metal-support interactions on nanoparticle catalysts and for tuning activity and selectivity. Using a combined experimental and theoretical approach, we studied the activation of H 2 and the effect of CO poisoning on isolated Rh atoms completely or partially covered by a copper oxide (Cu 2 O) thin film. Temperature-programmed desorption (TPD) experiments conducted in ultra-high vacuum (UHV) show that neither a partially nor a fully oxidized Cu 2 O layer grown on a Rh/Cu(111) single-atom alloy can activate hydrogen in UHV. However, in situ ambient pressure X-ray photoelectron spectroscopy (AP-XPS) experiments performed at elevated H 2 pressures reveal that Rh significantly accelerates the reduction of these Cu 2 O thin films by hydrogen. Remarkably, the fastest reduction rate is observed for the fully oxidized sample with all Rh sites covered by Cu 2 O. Both TPD and AP-XPS data demonstrate that these covered Rh sites are inaccessible to CO, indicating that Rh under Cu 2 O is active for H 2 dissociation but cannot be poisoned by CO. In contrast, an incomplete oxide film leaves some of the Rh sites exposed and accessible to CO, and hence prone to CO poisoning. Density functional theory calculations demonstrate that unlike many reactions in which hydrogen activation is rate limiting, the rate-determining step in the dissociation of H 2 on thin-film Cu 2 O with Rh underneath is the adsorption of H 2 on the buried Rh site, and once adsorbed, the dissociation of H 2 is barrierless. These calculations also explain why H 2 can only be activated at higher pressures. Together, these results highlight how different the reactivity of atomically dispersed Rh in Cu can be depending on its accessibility through the oxide layer, providing a way to engineer Rh sites that are active for hydrogen activation but resilient to CO poisoning.
Modular multi-interface nanocrystals for enhanced ethanol oxidation electrocatalysis
Electrochemical processes that utilize biomass-derived ethanol as a source of electrons and protons offer a sustainable energy strategy, yet their practical implementation is limited by sluggish ethanol oxidation reaction (EOR) kinetics and catalyst poisoning. Here, in this study, we report a modular multi-interface nanocrystal catalyst comprising core/shell Co 2 P/Pd and Pd-Au heterostructured interfaces that exhibit complementary functions for the enhanced EOR catalysis. The Co 2 P/Pd interface boosts Pd atom utilization and lowers the kinetic barriers for ethanol-to-acetate conversion, while the Pd-Au interface effectively alleviates CO poisoning caused by C–C bond cleavage of ethanol. In-depth analyses using in situ attenuated total reflectance-surface-enhanced infrared absorption spectroscopy, differential electrochemical mass spectrometry, and density functional theory calculations elucidate the mechanistic roles of these interfaces. The optimized Co 2 P/Pd-Au 0.08 nanorods achieve an excellent mass activity, underscoring the potential of modular, multi-interface nanocrystals for advancing EOR catalysis and offering a generalizable strategy for broader catalytic innovations.
Continuity of reaction kinetics across the pressure and materials gaps in CO oxidation on FeO–Pt interfaces
Translating atomic-scale insights from surface science studies of model catalysts to practical powder catalysts remains a persistent challenge in heterogeneous catalysis. Here, in this study, we demonstrate mechanistic continuity across the pressure and materials gaps during CO oxidation at the FeO-Pt interface using in situ microscopy, spectroscopy and computational modelling. Under reaction conditions, coordinatively unsaturated Fe (Fe cus ) sites at the interface enable selective O 2 activation on CO-saturated surfaces, circumventing the CO-poisoning limitation of platinum-group metals. We identify parallel reaction pathways involving the *O 2 -*CO intermediate. Remarkably, activation energies remain consistent at 12-15 kJ mol −1 (0.12-0.16 eV) from ultrahigh vacuum to atmospheric pressures and from FeO/Pt(111) model catalysts to FeO/Pt powder catalysts, validating mechanistic insights derived from surface science studies. Our findings show an example of bridging the long-standing divide between model and practical catalyst systems, establishing an effective approach to capture catalytic behaviours under operational conditions and advancing mechanism-driven catalyst design.
Quantum Monte Carlo Benchmarking of Molecular Adsorption on Graphene-Supported Single Pt Atom
The precise understanding of adsorption energetics and molecular geometry at catalytic sites is fundamental for advancing catalysis, particularly under the constraints of resource efficiency and environmental sustainability. Here, this study benchmarks the performance of density functional theory (DFT) calculations against diffusion Monte Carlo (DMC) calculations for adsorption properties of small gas molecules relevant to CO oxidation—namely O 2 , CO, CO 2 , and atomic oxygen—on a single Pt atom supported by pristine graphene. Our findings reveal that DMC calculations provide a significantly different landscape of adsorption energetics compared to DFT results. Notably, DFT predicts different lowest-energy configurations and spin states, particularly for O 2 , which suggests potential discrepancies in predicting the catalytic behavior. Furthermore, this study identifies the critical issue of CO poisoning, highlighted by the large disparity between the DMC adsorption energies of O 2 (−1.23(2) eV) and CO (−3.37(1) eV), which can inhibit the catalytic process. These results emphasize the necessity for more sophisticated computational approaches in catalysis research, aiming to refine the prediction accuracy of reaction mechanisms and to enhance the design of more effective catalysts.
Embedding Reverse Electron Transfer Between Stably Bare Cu Nanoparticles and Cation‐Vacancy CuWO 4
Cu nanoparticles (NPs) have attracted widespread attention in electronics, energy, and catalysis. However, conventionally synthesized Cu NPs face some challenges such as surface passivation and agglomeration in applications, which impairs their functionalities in the physicochemical properties. Here, the issues above by engineering an embedded interface of stably bare Cu NPs on the cation-vacancy CuWO 4 support is addressed, which induces the strong metal-support interactions and reverse electron transfer. Various atomic-scale analyses directly demonstrate the unique electronic structure of the embedded Cu NPs with negative charge and anion oxygen protective layer, which mitigates the typical degradation pathways such as oxidation in ambient air, high-temperature agglomeration, and CO poisoning adsorption. Kinetics and in situ spectroscopic studies unveil that the embedded electron-enriched Cu NPs follow the typical Eley-Rideal mechanism in CO oxidation, contrasting the Langmuir-Hinshelwood mechanism on the traditional Cu NPs. This mechanistic shift is driven by the Coulombic repulsion in anion oxygen layer, enabling its direct reaction with gaseous CO to form the easily desorbed monodentate carbonate.
Theoretical and Experimental Insights into CO 2 Capture and Methanation over Amine-Grafted Ru-Based Catalysts
Carbon capture and storage (CCS) technologies, along with CO 2 capture and conversion methods, have emerged as crucial research areas to address rising CO 2 emissions. In this study, we seek to understand the mechanistic role of amines in enabling lower-energy pathways for CO 2 conversion. Our research focuses on the development and analysis of dual-functional materials (DFMs) engineered for the reactive capture and conversion (RCC) of CO 2 into methane, utilizing Ru catalysts grafted with amine groups. We employ Density Functional Theory (DFT) calculations using methylamine as a model amine to investigate the impact of amine groups on CO 2 methanation on a Ru(0001) surface, both in the presence and absence of amine groups. The amine ligand alters the carbon coordination environment, promoting direct C–O dissociation and potentially destabilizing the CO* adsorbate, thereby reducing the risk of CO poisoning. Additionally, we observe a preference for hydrogenation, although it becomes more energetically uphill in the amine-bound scenario. Our experiments, however, report similar CO 2 conversion and CH 4 production rates over the synthesized catalysts “Ru/TiO 2 ” and the amine (N-(2-aminoethyl)-3-aminoproplytrimethoxysilane (“diaminosilane”)) deposited catalyst “Diamine−Ru/TiO 2 ”. By constructing comparative reaction-free energy diagrams and performing microkinetic modeling (MKM) simulations, we link our theoretical findings with experimentally observed CO 2 uptake, conversion, and methane production rates. A microkinetic model was employed to investigate the anomaly, showing reduced amine–carbon complex coverage and increased CO 2 coverage at all temperatures. The MKM simulations consistently confirmed these trends. In conclusion, this comprehensive approach offers key insights into the role of the amine-CO 2 bond in methanation, highlighting a pathway toward lower-energy, more efficient CO 2 capture and conversion processes.
Mesoporous PdAg Nanospheres for Stable Electrochemical CO 2 Reduction to Formate
Palladium is a promising material for electrochemical CO 2 reduction to formate with high Faradaic efficiency near the equilibrium potential. It unfortunately suffers from problematic operation stability due to CO poisoning on surface. In this work, it is demonstrated that alloying is an effective strategy to alleviate this problem. Mesoporous PdAg nanospheres with uniform size and composition are prepared from the co-reduction of palladium and silver precursors in aqueous solution using dioctadecyldimethylammonium chloride as the structure-directing agent. The best candidate can initiate CO 2 reduction at zero overpotential and achieve high formate selectivity close to 100% and great stability even at <-0.2 V versus reversible hydrogen electrode. The high selectivity and stability are believed to result from the electronic coupling between Pd and Ag, which lowers the d-band center of Pd and thereby significantly enhances its CO tolerance, as evidenced by both electrochemical analysis and theoretical simulations.
Achieving Ultra-High Selectivity to Hydrogen Production from Formic Acid on Pd–Ag Alloys
Palladium-silver based alloy catalysts have a great potential for CO-free hydrogen production from formic acid for fuel cell applications. However, the structural factors affecting the selectivity of formic acid decomposition is still debated. Herein, the decomposition pathways of formic acid on Pd-Ag alloys with different atomic configurations have been investigated to identify the alloy structures yielding high H 2 selectively. Several Pd x Ag 1-x surface alloys with various compositions were generated on a Pd(111) single crystal; their atomic distribution and electronic structure were determined by a combination of infrared reflection absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT). It was established that the Ag atoms with Pd neighbors are electronically altered, and the degree of alteration correlates with the number of nearest Pd. Temperature programmed reaction spectroscopy (TPRS) and DFT demonstrated that the electronically altered Ag domains create a new reaction pathway that selectively dehydrogenates formic acid. In contrast, Pd monomers surrounded by Ag are demonstrated to have a similar reactivity compared to pristine Pd(111), yielding CO and H 2 O in addition to the dehydrogenation products. Furthermore, they bind to the produced CO weaker than pristine Pd, demonstrating an enhancement in resistance to CO poisoning. This work therefore shows that surface Ag domains modified by interaction with subsurface Pd are the key active sites for selective decomposition of formic acid, while surface Pd atoms are detrimental for selectivity. Hence the decomposition pathways can be tailored for CO-free H 2 production on Pd-Ag alloy systems.
Single-atom Rh/N-doped carbon electrocatalyst for formic acid oxidation
To meet the requirements of potential applications, it is of great importance to explore new catalysts for formic acid oxidation that have both ultra-high mass activity and CO resistance. In this work, we successfully synthesize atomically dispersed Rh on N-doped carbon (SA-Rh/CN) and discover that SA-Rh/CN exhibits promising electrocatalytic properties for formic acid oxidation. The mass activity shows 28- and 67-fold enhancements compared with state-of-the-art Pd/C and Pt/C, respectively, despite the low activity of Rh/C. Interestingly, SA-Rh/CN exhibits greatly enhanced tolerance to CO poisoning, and Rh atoms in SA-Rh/CN resist sintering after long-term testing, resulting in excellent catalytic stability. Density functional theory calculations suggest that the formate route is more favourable on SA-Rh/CN. According to calculations, the high barrier to produce CO, together with the relatively unfavourable binding with CO, contribute to its CO tolerance.
Pd3Ag(111) as a Model System for Hydrogen Separation Membranes: Combined Effects of CO Adsorption and Surface Termination on the Activation of Molecular Hydrogen
Abstract The co-adsorption of hydrogen and carbon monoxide on Pd 3 Ag(111) alloy surfaces has been studied as a model system for Pd-Ag alloys in membrane and catalysis applications using periodic density functional theory calculations (PW91-GGA). We explored the effects of Pd–Ag surface composition, since segregation of silver towards and away from the surface has been suggested to explain the experimentally observed changes in H 2 activation, CO inhibition and reactivity. We found that CO pre-adsorbed on the surface weakens the adsorption of H on Pd 3 Ag(111) alloy surfaces irrespective of whether the surface termination corresponds to the bulk Pd 3 Ag composition, or is purely Pd-terminated. A higher coverage of H with CO present is obtained for the Pd-terminated surface; this surface also exhibits a larger range of chemical potentials for co-adsorbed hydrogen and CO. The barrier for H 2 activation increases with increasing CO coverage, but the surface composition has the largest impact on H 2 activation at intermediate CO coverage. The results imply that Pd-based membranes with typically ~ 23 wt% Ag are less prone to CO poisoning if the surface becomes Pd-terminated.
Intra-catalyst CH 4 oxidation pathways on a Pd/Al 2 O 3 /CeZrO x -based commercial catalyst and implications on NO x conversion profiles for a natural gas vehicle exhaust under lambda modulation
The performance of a three-way catalyst (TWC) in natural gas-powered vehicles is enhanced by periodic changes in air-to-fuel ratio (λ-modulation). The reaction networks and sequences inside the catalyst that facilitate such enhanced performance have not been extensively investigated. Here, this work applied intra-catalyst measurements (SpaciMS) to analyze the transient spatiotemporal gas concentrations inside a Pd-based TWC to establish relationships between CH 4 , NO x , CO and H 2 conversion pathways. Steam reforming and partial oxidation were revealed to be the main CH 4 conversion routes. The cyclic rich-lean conditions combined with the oxygen storage capacity (OSC) of the TWC generate reduced and oxidized zones that are constantly moving within the catalyst, changing the dominant chemical reactions occurring on the surface. In the reduced zones, OSC is depleted while CH 4 is converted through steam reforming and NO x is converted through reactions with H 2 , CO, and other surface-bound reducing fragments formed by CH 4 conversion. In the oxidized zones, OSC is replenished, CH 4 is converted by partial oxidation, and H 2 , CO, and NH 3 are oxidized. The length of lean-rich phases impacts the catalyst performance significantly; too short or too long of a rich or lean phase can lower the overall conversion of reactive species. An inhibition of CH 4 conversion was observed during the rich phase possibly due to CO-poisoning of active sites. The intra-catalyst measurements revealed that the catalyst consists of three distinct reaction zones and their lengths vary with modulation conditions. Various modulation frequencies, amplitudes, λ-centers, and temperatures were investigated which allowed an understanding of how these parameters affect the reaction zones and catalyst utilization. Understandings from this work can enable adaptive λ-control strategies to optimize the overall TWC performance over a range of vehicle operating conditions.
Effect of dilute Rh on oxygen dissociation, spillover, and the oxidation of Cu across many orders of magnitude pressure
Knowledge of how trace amounts of more reactive metals influence the oxidation rate and mechanism of Cu surfaces is essential for developing strategies to optimize the performance of Cu-based catalysts. We find that the addition of 1% Rh to Cu(111) increases the initial O 2 dissociation rate by approximately 9-fold. CO poisoning experiments reveal that single Rh atoms activate O 2 and facilitate the spillover of atomic oxygen to Cu sites. Scanning tunneling microscopy (STM) and in situ X-ray photoelectron spectroscopy (XPS) support this mechanism, showing enhanced surface oxygen near Rh atoms. Here, a density functional theory (DFT)-based model demonstrates that Rh binds the O 2 precursor 0.15 eV more strongly than Cu(111) and lowers the O 2 dissociation barrier by 0.02 eV. Both single-crystal and nanoparticle experiments show that at low oxygen pressures, Rh enhances Cu oxidation, whereas at higher pressures, it inhibits deeper oxidation, as evidenced by in situ ultraviolet-visible (UV-vis) spectra.
Single-Atom Alloy Catalysis
Single-Atom Alloys (SAAs) play an increasingly significant role in the field of single-site catalysis and are typically composed of catalytically active elements atomically dispersed in more inert, but more catalytically selective host metals. SAAs have been shown to catalyze a range of industrially important reactions in thermal, photo- and electro-catalysis studies. Due to the unique geometry of SAAs, the location of the transition state and the binding site of reaction intermediates are often decoupled, which can enable both facile dissociation of reactants and weak binding of intermediates, two key factors for efficient and selective catalysis. Often, this results in deviations from transition metal scaling relationships that limit conventional catalysts. SAAs also offer reduced susceptibility to CO poisoning, cost savings from reduced precious metal usage, opportunities for bifunctional mechanisms via spillover, and higher resistance to deactivation by coking that plagues many industrial catalysts. In this review, we begin by introducing SAAs and describe how model systems and real catalysts can be prepared and characterized. Finally, we then review all available SAA literature on a per reaction basis before concluding with a description of the general properties of this new class of heterogeneous catalysts and presenting opportunities for future research and development.
PtRu Catalysts on Nitrogen-Doped Carbon Nanotubes with Conformal Hydrogenated TiO 2 Shells for Methanol Oxidation
The methanol oxidation reaction (MOR) is the limiting factor in direct methanol fuel cells (DMFC). There is an urgent need to improve the catalytic activity and stability of MOR catalysts. This study reports a highly active PtRu catalyst for MOR based on a hybrid multifunctional catalyst support consisting of a conformal amorphous hydrogenated TiO 2 shell wrapped around the oxygenated N-doped carbon nanotube core, denoted as PtRu/TiO 2 / ONCNT-400. Both the TiO 2 shell and the subsequent PtRu nanoparticles are deposited by a rapid microwave-assisted synthesis processes. The hydrogenated TiO 2 shell is found to exhibit a strong interaction with the deposited PtRu catalyst nanoparticles and effectively prevent them from agglomeration during the postdeposition thermal annealing to form more active crystalline PtRu alloy catalysts. In addition, the defective hydrogenated TiO 2 shell enhances the PtRu catalyst activity by the synergistic effects of partial charge transfer from TiO 2 to PtRu and high oxophilicity, which improves the kinetics of oxidation of poisonous CO intermediate to CO 2 . The mass activity for MOR and long-cycling stability of the PtRu/TiO 2 /ONCNT-400 catalyst surpass the two benchmark commercial PtRu/C catalysts from Johnson Matthey (JM) and Tanaka KiKinzoku (TKK), respectively. Furthermore, the results demonstrate that PtRu/TiO 2 /ONCNT-400 can serve as an efficient catalyst for MOR in DMFC.