High pressure microreactor for minute amounts of catalyst on planar supports: a case study of CO2 hydrogenation over Pd0.25Zn0.75Ox nanoclusters DOI Creative Commons
Imran Abbas, Filippo Romeggio, Kacper Pilarczyk

et al.

Published: Aug. 16, 2024

High-pressure studies of catalyst quantities down to a few hundred nanograms, particularly well-defined catalysts prepared using physical methods in ultra-high vacuum on planar supports can potentially bridge the surface science and applied catalysis approaches development. However, chemical reactors required for such investigations are lacking. We present novel design evaluation 50 µL rectangular microchannel reactor capable testing small at pressures up 40 bar temperatures 250°C. To evaluate microreactor's performance, Pd0.25Zn0.75Ox nanoclusters soft-landed SiO2-coated mica sheets cluster beam deposition technique, were tested reverse water-gas shift reaction through series kinetic experiments. Experimental results, combined with computational fluid dynamics mass transport analysis, demonstrate that proposed microreactor setup allows minute high sensitivity industrially relevant pressures. Although not restricted particular preparation method, is an excellent platform conducting catalytic tests composition-controlled, mass-selected, gas-phase nanoparticles deposited substrates, facilitating development reliable structure-activity relationships enabling more rational catalysts.

Language: Английский

The Enigma of Methanol Synthesis by Cu/ZnO/Al2O3-Based Catalysts DOI
Arik Beck, Mark A. Newton, Leon G. A. van de Water

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(8), P. 4543 - 4678

Published: April 2, 2024

The activity and durability of the Cu/ZnO/Al

Language: Английский

Citations

40
Hydrogenation of CO 2 for sustainable fuel and chemical production DOI
Jingyun Ye, Nikolaos Dimitratos, Liane M. Rossi

et al.

Science, Journal Year: 2025, Volume and Issue: 387(6737)

Published: Feb. 27, 2025

Catalytic carbon dioxide (CO2) hydrogenation is a potential route for producing sustainable fuels and chemicals, but existing catalysts need improvement. In particular, identifying active sites understanding the interaction between components dynamic behavior of participant species remain unclear. This fundamental knowledge essential design more efficient stable catalysts. Because nature site (metal, oxide, carbide) main factor that determines catalytic activity catalysts, this Review focuses on various types heterogeneous have been recently reported in literature as CO2 conversion to C1 [carbon monoxide (CO), methanol (CH3OH), methane (CH4)], higher hydrocarbons. We focus establishing key connections active-site structures selectivity, regardless catalyst composition.

Language: Английский

Citations

3
A New Look at Catalyst Surfaces at Work: Introducing Mixed Isotope Operando Infrared Spectroscopy (MIOIRS) DOI Creative Commons
Matteo Monai

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1363 - 1386

Published: Jan. 8, 2025

This Perspective focuses on the characterization of supported metal catalysts by operando and CO infrared (IR) spectroscopy. IR spectroscopy is a powerful technique for probing catalyst surfaces used to identify single-atom catalysts, estimate surface availability gas phase, measure Lewis acidity. However, interpretation spectra not trivial influenced dipole–dipole interactions among molecules at medium high coverage. Such phenomenon results in spectral distortions, such as intensity transfer bands, appearance spurious shifts band position. Dipole–dipole were widely investigated understood from 1950s 1990s, but implications have been seemingly overlooked literature, with few exceptions. Inspired seminal studies field, I propose here use mixed isotopic streams, diluted 13CO 12CO, reduce dipole coupling effects retrieve more information reactions involving CO, oxidation or hydrogenation reactions. Similarly, 13CO2/12CO2 streams may be applied CO2 hydrogenation, where adsorbed commonly observed. The proposed name Mixed Isotope Operando Spectroscopy, MIOIRS. In this Perspective, will first summarize nature layers their spectra. Then, briefly describe how mixtures can partially break adsorbates distortion. both sections, give showcases vibrational heterogeneous catalysts. Finally, discuss possible MIOIRS detection quantification defect sites nanoparticles, bimetallic nanoparticles surfaces, kinetics intermediates different active sites. Notably, expanded other which strong permanent dipoles, self-catalytic reduction NOx abatement.

Language: Английский

Citations

1
Reaction Mechanisms and Applications of Single Atom Catalysts for Thermal-Catalytic Carbon Dioxide Hydrogenation Toward Oxygenates DOI
Fei Wang, Yicheng Liu,

Mengke Peng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(21), P. 16434 - 16458

Published: Oct. 23, 2024

Thermo-catalytic CO2 hydrogenation to high-value oxygenates has been regarded as one of the most powerful strategies that can potentially alleviate excessive emissions. However, due high chemical stability and variability pathways, it is still challenging achieve highly active selective hydrogenation. Single atom catalysts (SACs) with ultrahigh metal utilization efficiency extraordinary electronic features have displayed growing importance for thermo-catalytic multiple developed improve performances. Here, we review breakthroughs in developing SACs efficient toward common (CO, HCOOH, CH3OH, CH3CH2OH) following order: first, an analysis reaction mechanisms thermodynamics challenges reactions; second, a summary SAs designed by dividing them into two categories single- dual-sites; third, discussion support effects focus on approaches regulating strong metal–support interaction (MSI). Summarily, current future perspectives develop higher-performance are presented. We expect this bring more design inspiration trigger innovation catalytic evolution materials eventually benefit achievement carbon-neutrality goal.

Language: Английский

Citations

7
Design Principles of Catalytic Materials for CO2 Hydrogenation to Methanol DOI Creative Commons
Thaylan Pinheiro Araújo, Sharon Mitchell, Javier Pérez‐Ramírez

et al.

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 19, 2024

Abstract Heterogeneous catalysts are essential for thermocatalytic CO 2 hydrogenation to methanol, a key route sustainable production of this vital platform chemical and energy carrier. The primary catalyst families studied include copper‐based, indium oxide‐based, mixed zinc–zirconium oxides‐based materials. Despite significant progress in their design, research is often compartmentalized, lacking holistic overview needed surpass current performance limits. This perspective introduces generalized design principles catalytic materials ‐to‐methanol conversion, illustrating how complex architectures with improved functionality can be assembled from simple components (e.g., active phases, supports, promoters). After reviewing basic concepts ‐based methanol synthesis, engineering explored, building complexity single binary ternary systems. As nanostructures strongly depend on reaction environment, recent operando characterization techniques machine learning approaches examined. Finally, common rules centered around symbiotic interfaces integrating acid–base redox functions role optimization identified, pinpointing important future directions methanol.

Language: Английский

Citations

6
Exploring catalyst developments in heterogeneous CO2 hydrogenation to methanol and ethanol: A journey through reaction pathways DOI Creative Commons
Rasoul Salami, Yimin Zeng, Xue Han

et al.

Journal of Energy Chemistry, Journal Year: 2024, Volume and Issue: 101, P. 345 - 384

Published: Oct. 10, 2024

Language: Английский

Citations

5
Gallium: A Universal Promoter Switching CO2 Methanation Catalysts to Produce Methanol DOI Creative Commons
Wei Zhou, Colin Hansen, Weicheng Cao

et al.

JACS Au, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 20, 2024

Hydrogenation of CO2 to methanol is foreseen as a key step close the carbon cycle. In this study, we show that introducing Ga into silica-supported nanoparticles based on group 8-9 transition noble metals (M = Ru, Os, Rh, and Ir - MGa@SiO2) switches their reactivity from producing mostly methane (sel. > 97%) (>50% CH3OH/DME sel.) alongside CO only byproduct. These catalysts, prepared via surface organometallic chemistry (SOMC) approach, consist small, alloyed, narrowly distributed MGa nanoparticles, evidenced by X-ray absorption spectroscopy (XAS) adsorption studies. Notably, detailed in situ XAS diffuse reflectance Fourier transform infrared (DRIFTS) studies complemented with density functional theory (DFT) calculations indicate generates stable bulk alloys. The alloys persist during hydrogenation according XAS, resulting suppressed methanation. Meanwhile, small fraction GaO x thereby MGa-GaO interfaces are formed, IR spectroscopy, likely responsible for stabilizing methoxy intermediates favoring formation.

Language: Английский

Citations

5
Mechanistic and kinetic relevance of hydrogen and water in CO2 hydrogenation on Cu-based catalysts DOI
Ting Lin, Michelle A. Nolen, Carrie A. Farberow

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115936 - 115936

Published: Jan. 1, 2025

Language: Английский

Citations

0
Growth and mobility of copper in industrial Cu/ZnO/Al2O3 hydrogenation catalyst investigated by in situ gas-cell scanning transmission electron microscopy DOI Creative Commons
Xiansheng Li, Henrik Eliasson, Walid Dachraoui

et al.

Applied Surface Science, Journal Year: 2025, Volume and Issue: unknown, P. 162321 - 162321

Published: Jan. 1, 2025

Language: Английский

Citations

0
Influence of zinc oxide nanoparticles on the carbon accumulation on silver exposed to carbon dioxide hydrogenation reaction conditions DOI Creative Commons
Peter Leidinger, Mirco Panighel, Vitaly L. Sushkevich

et al.

Nanoscale, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The strong influence of surface adsorbates on the morphology a catalyst is exemplified by studying silver with and without deposited zinc oxide nanoparticles upon exposure to reaction gases used for carbon dioxide hydrogenation. Ambient pressure X-ray photoelectron spectroscopy scanning tunneling microscopy measurements indicate accumulation deposits at 200 °C. While oxygen-free species observed pure show interaction decorate atomic steps surface, this decoration not oxygen-containing additional nanoparticles. Annealing sample temperatures above 350 °C removes contaminants hydrogenation methane.

Language: Английский

Citations

0