Low-nuclearity single-atom and supported metal cluster catalysts in ethylene and propylene hydroformylation Marcos G. Farpón, Gonzalo Prieto Catalysis Today, 2025 Olefin hydroformylation is one of the most significant examples of homogeneously catalyzed conversion processes. However, developing chemo/regio-selective and stable solid catalysts has remained a persistent challenge in heterogeneous catalysis . Particularly the design of solid catalysts for the hydroformylation of light, gaseous olefins, such as ethylene and propylene , has been extensively researched, given that the products from these processes are key players in the oxo-chemicals market. Additionally, developing selective, continuous gas-solid C 2–3 olefin hydroformylation processes prospectively offers a reactive separation alternative to conventional and massively energy-intensive cryogenic distillation separation methods. In this review, we first assess the potential of reductive olefin hydroformylation as a cost-effective alternative to conventional cryogenic distillation processes for recovering value from industrial gas mixtures of ethylene and propylene . Taking a conventional ethylene splitter as a reference case, a reactive separation through ethylene reductive hydroformylation to 1-propanol is predicted to provide significant savings in terms of utility costs. Next, major advances in the design and development of solid catalysts for ethylene and propylene hydroformylation are surveyed, with an emphasis on single-atom catalysts (SACs) and supported metal nanoclusters . These catalysts have recently achieved hydroformylation activity and chemo/regio selectivity comparable to, or even surpassing, those traditionally exclusive to free molecular catalysts in solution. Different catalyst design strategies, including the heterogenization of metal coordination complexes in supported ionic liquid phase (SILP) catalysts and porous organic ligands (POLs), as well as the tuning of oxide-supported catalysts via the adjustment of metal-oxide interfacial effects or through nanoconfinement within zeolitic frameworks, are systematically reviewed and compared. Finally, conclusions are provided, alongside a critical perspective on fundamental and practical aspects that require particular attention to ensure rational and systematic progress toward optimized catalysts and reaction settings, ultimately paving the way for the heterogenization of light olefin hydroformylation processes.
“Heating where it hurts”: Electromagnetic induction remote energy transfer to a solid catalyst enables waste polymer upcycling Marcos G. Farpón, Enrique Torregrosa, Gonzalo Prieto Materials Today Catalysis, 2024 Electromagnetic induction heating currently attracts significant attention as a means to electrify catalytic processes and leverage a highly specific and localized energy supply. This Comment article features the application of this unconventional energy input for waste polymer conversion to fuel hydrocarbons.
Multifunctional materials for catalyst-specific heating and thermometry in tandem catalysis Marcos G. Farpón, Raquel Peláez, Verónica Recio, Burak Atakan, Carlos Zaldo, Gonzalo Prieto Journal of Materials Chemistry A, 2023 A multifunctional material design, integrating catalytic and auxiliary magnetic susception and contactless thermal sensing functionalities, unlocks catalyst-specific heating and thermometry for spatially proximate solid catalysts in a single reactor.
Rhodium Single-Atom Catalyst Design through Oxide Support Modulation for Selective Gas-Phase Ethylene Hydroformylation Marcos G. Farpón, Wilson Henao, Philipp N. Plessow, Eva Andrés, Raúl Arenal, Carlo Marini, Giovanni Agostini, Felix Studt, Gonzalo Prieto Angewandte Chemie International Edition, 2023 A frontier challenge in single‐atom (SA) catalysis is the design of fully inorganic sites capable of emulating the high reaction selectivity traditionally exclusive of organometallic counterparts in homogeneous catalysis. Modulating the direct coordination environment in SA sites, via the exploitation of the oxide support's surface chemistry, stands as a powerful albeit underexplored strategy. We report that isolated Rh atoms stabilized on oxygen‐defective SnO2 uniquely unite excellent TOF with essentially full selectivity in the gas‐phase hydroformylation of ethylene, inhibiting the thermodynamically favored olefin hydrogenation. Density Functional Theory calculations and surface characterization suggest that substantial depletion of the catalyst surface in lattice oxygen, energetically facile on SnO2, is key to unlock a high coordination pliability at the mononuclear Rh centers, leading to an exceptional performance which is on par with that of molecular catalysts in liquid media.
Supported Metal Single-Atom Thermocatalysts for the Activation of Small Molecules Marcos G. Farpón, Wilson Henao, Gonzalo Prieto Supported Metal Single Atom Catalysis, 2022 The activation and selective valorization of small molecules such as H 2 O, CH 4 , CO x , N 2 are expected to play a central role in the shift needed by the chemical industry basis, to solve sustainability issues associated with the current use of crude oil as the universal feedstock. However, activating these generally recalcitrant and unreactive molecules, and selectively steering their conversion pathways face important kinetic hurdles. With emphasis on conversion processes driven by temperature, i.e. lacking additional stimuli such as a voltage bias or light irradiation, for the conversion of C 1 molecules (CH 4 , CO 2 , and CO), this chapter discusses the benefits and drawbacks anticipated for monoatomic metal active sites in oxide-supported single-atom catalysts (SACs) compared to their polynuclear metal aggregate counterparts. The fundamentals underlying the activation of these simple molecules are succinctly discussed. Then, achievements attained in their selective conversion with supported, atomically dispersed metal catalysts are reviewed. Success cases, which have already reached industrial interest, are highlighted. In other cases, major challenges remaining in the way toward performances of technical interest are identified. The chapter additionally underscores how the dynamic fluxionality observed for those monoatomic sites on SACs calls for the development and application of high-sensitivity operando physicochemical methods, to track their structure prior to, during, and after catalytic action, to draw solid conclusions on the structure of the active metal species responsible for the catalytic performances observed macroscopically.
Bottom-up assembly of bimetallic nanocluster catalysts from oxide-supported single-atom precursors Bidyut B. Sarma, Giovanni Agostini, Marcos G. Farpón, Carlo Marini, Norbert Pfänder, Gonzalo Prieto Journal of Materials Chemistry A, 2021 Oxidative re-dispersion of two metals (Pd and Pt), as single-atoms, within nanometer distances on a common oxide carrier (MgO) delivers, upon reductive agglomeration, small (ca. 1 nm) bimetallic cluster catalysts with remarkable stability.
RECENT SCHOLAR PUBLICATIONS
Alloying Effects in Pt-Ag Catalysts Towards Selective Ethylene to 1-Propanol Direct Conversion Via Tandem Catalysis MG Farpón, T Rodenas, V Recio, E Andres, R Arenal, G Prieto 2025 AIChE Annual Meeting , 2025 2025
Low-nuclearity single-atom and supported metal cluster catalysts in ethylene and propylene hydroformylation MG Farpón, G Prieto Catalysis Today 445, 115052 , 2025 2025 Citations: 2
“Heating where it hurts”: Electromagnetic induction remote energy transfer to a solid catalyst enables waste polymer upcycling MG Farpón, E Torregrosa, G Prieto Materials Today Catalysis 6, 100059 , 2024 2024 Citations: 3
Proceso catalítico gas-sólido de conversión de olefina en alcohol G Prieto, MG Farpón 2024
Gas-solid catalytic process for converting an olefin into alcohol G Prieto, MG Farpón 2024
Tandem catalytic processes for selective ethylene valorization into C3 chemicals MG Farpón Universitat Politècnica de València , 2024 2024
Fully-Selective Gas-Phase Ethylene Hydroformylation on a Rh1/SnO2 Single-Atom Catalyst MG Farpón, W Henao, PN Plessow, E Andrés, R Arenal, C Marini, ... https://nam.confex.com/nam/2023/meetingapp.cgi/Paper/30766 , 2023 2023
Direct Synthesis of Acetone from Syngas and Dimethyl Ether V ia Tandem Carbonylation-Ketonization Catalysis E Andrés, R Peláez, A Rielves, W Henao, MG Farpón, G Prieto The 28th North American Catalysis Society Meeting , 2023 2023
Rhodium single‐atom catalyst design through oxide support modulation for selective gas‐phase ethylene hydroformylation MG Farpón, W Henao, PN Plessow, E Andrés, R Arenal, C Marini, ... Angewandte Chemie International Edition 62 (1), e202214048 , 2023 2023 Citations: 82
Multifunctional materials for catalyst-specific heating and thermometry in tandem catalysis MG Farpón, R Peláez, V Recio, B Atakan, C Zaldo, G Prieto Journal of Materials Chemistry A 11 (37), 19854-19859 , 2023 2023 Citations: 15
Proceso de producción de acetona G Prieto, E Andrés, MG Farpón 2022
Supported Metal Single‐Atom Thermocatalysts for the Activation of Small Molecules MG Farpón, W Henao, G Prieto Supported Metal Single Atom Catalysis, 425-472 , 2022 2022 Citations: 2
Bottom-up assembly of bimetallic nanocluster catalysts from oxide-supported single-atom precursors BB Sarma, G Agostini, MG Farpón, C Marini, N Pfänder, G Prieto Journal of Materials Chemistry A 9 (13), 8401-8415 , 2021 2021 Citations: 20
Development of novel thermogenic and thermometry methods towards tandem catalysis MG Farpón Universidad de Oviedo , 2018 2018 Citations: 1
MOST CITED SCHOLAR PUBLICATIONS
Rhodium single‐atom catalyst design through oxide support modulation for selective gas‐phase ethylene hydroformylation MG Farpón, W Henao, PN Plessow, E Andrés, R Arenal, C Marini, ... Angewandte Chemie International Edition 62 (1), e202214048 , 2023 2023 Citations: 82
Bottom-up assembly of bimetallic nanocluster catalysts from oxide-supported single-atom precursors BB Sarma, G Agostini, MG Farpón, C Marini, N Pfänder, G Prieto Journal of Materials Chemistry A 9 (13), 8401-8415 , 2021 2021 Citations: 20
Multifunctional materials for catalyst-specific heating and thermometry in tandem catalysis MG Farpón, R Peláez, V Recio, B Atakan, C Zaldo, G Prieto Journal of Materials Chemistry A 11 (37), 19854-19859 , 2023 2023 Citations: 15
“Heating where it hurts”: Electromagnetic induction remote energy transfer to a solid catalyst enables waste polymer upcycling MG Farpón, E Torregrosa, G Prieto Materials Today Catalysis 6, 100059 , 2024 2024 Citations: 3
Low-nuclearity single-atom and supported metal cluster catalysts in ethylene and propylene hydroformylation MG Farpón, G Prieto Catalysis Today 445, 115052 , 2025 2025 Citations: 2
Supported Metal Single‐Atom Thermocatalysts for the Activation of Small Molecules MG Farpón, W Henao, G Prieto Supported Metal Single Atom Catalysis, 425-472 , 2022 2022 Citations: 2
Development of novel thermogenic and thermometry methods towards tandem catalysis MG Farpón Universidad de Oviedo , 2018 2018 Citations: 1
Alloying Effects in Pt-Ag Catalysts Towards Selective Ethylene to 1-Propanol Direct Conversion Via Tandem Catalysis MG Farpón, T Rodenas, V Recio, E Andres, R Arenal, G Prieto 2025 AIChE Annual Meeting , 2025 2025
Proceso catalítico gas-sólido de conversión de olefina en alcohol G Prieto, MG Farpón 2024
Gas-solid catalytic process for converting an olefin into alcohol G Prieto, MG Farpón 2024
Tandem catalytic processes for selective ethylene valorization into C3 chemicals MG Farpón Universitat Politècnica de València , 2024 2024
Fully-Selective Gas-Phase Ethylene Hydroformylation on a Rh1/SnO2 Single-Atom Catalyst MG Farpón, W Henao, PN Plessow, E Andrés, R Arenal, C Marini, ... https://nam.confex.com/nam/2023/meetingapp.cgi/Paper/30766 , 2023 2023
Direct Synthesis of Acetone from Syngas and Dimethyl Ether V ia Tandem Carbonylation-Ketonization Catalysis E Andrés, R Peláez, A Rielves, W Henao, MG Farpón, G Prieto The 28th North American Catalysis Society Meeting , 2023 2023
Proceso de producción de acetona G Prieto, E Andrés, MG Farpón 2022
