ConspectusThe production of value-added chemicals from CO2 has been a thriving topic of research for the past few decades because of its contribution to a circular carbon economy. Combined with CO2 capture and storage, thermocatalytic hydrogenation of CO2 to CH3OH with green or blue hydrogen, offers an attractive route to mitigate CO2 emissions and to decarbonize the chemical industry. Numerous studies have been focused on catalysts based on supported metallic nanoparticles; these catalysts consist of at least one transition or coinage metal and a promoter element combined with an oxide support to disperse the active phase. Besides Zn-promoters used in Cu-based hydrogenation catalysts, numerous reports point to Ga as a promoter for methanol synthesis. In recent years, Ga has been shown to convert almost all transition metals toward selective methanol synthesis, but its specific role remains a topic of discussions.In this Account, we summarize how surface organometallic chemistry (SOMC) has enabled the discovery of novel catalysts and the development of detailed structure–activity relationships. Particularly, we show that Ga uniquely generates alloys with transition and coinage (Cu) metal elements across groups 8–11 and converts them into selective methanol synthesis catalysts. Specifically, we highlight the role of M–Ga alloy formation, alloy stability, and the formation of M(Ga)–GaOx interfaces under reaction conditions. This has been possible thanks to the combination of SOMC, which enables the formation of supported nanoparticles with tailored compositions and interfaces, and state-of-the-art characterization including operando techniques along with computational modeling, including ab initio molecular dynamic calculations. Dynamic alloying–dealloying behaviors under reaction conditions and the formation of M/MGa–GaOx interfaces are identified as key drivers for efficient methanol formation.

Si-doping is found to switch the reactivity of cobalt catalysts in CO2 hydrogenation from methanation to the reverse water–gas shift reaction. Using a surface organometallic chemistry approach, cobal...

Promotional effects are ubiquitous across catalytic processes involving supported nanoparticles, where additional elements, known as promoters, significantly enhance the catalytic performances (activity, selectivity, and/or stability) of nanoparticles. However, the inherent complexity of catalytic materials, comprising multiple species located both in the bulk and at the surface, makes it difficult to pinpoint the role of promoters at the molecular level. In this study, we disentangle the effect of alloying and interfacial sites in a low-temperature reverse water–gas shift (RWGS) reaction, a key process in the chemical industry, by precisely constructing catalysts featuring narrowly dispersed alloyed PtCr nanoparticles with or without Cr(III) interfacial sites. Notably, we show that a catalyst containing exclusively PtCr alloys, PtCr@SiO2, displays a substantial increase in catalytic activity compared to monometallic Pt@SiO2, while having additional Cr(III) interfacial sites (PtCr-Crint@SiO2) further improves the catalyst performance. In situ spectroscopic results reveal that the PtCr alloy facilitates a redox reaction pathway, whereas the presence of Cr(III) interfacial sites greatly facilitates CO2 adsorption and opens an additional formate-mediated pathway, further accelerating the reaction. These findings highlight the power of well-defined model systems in elucidating the promotional effects at the molecular level.

Konstantin Ivanov intercontinental magnetic resonance seminar series started on April 8, 2020. It organises seminars on a range of topics in magnetic resonance covering NMR, EPR, hyperpolarisation, co...

This Perspective summarizes the current state of the art in understanding the local environments of metal sites across homogeneous and heterogeneous catalysts by means of solid-state nuclear magnetic ...

Research could improve single-atom catalyst design

Research could improve single-atom catalyst design

The reverse water–gas shift (RWGS) reaction is a pivotal industrial process that is central to CO2 utilization. It typically relies on rare platinum group metal catalysts and high temperatures (over 1...

The exploitation of shale gas has stimulated the use of on-purpose propane dehydrogenation (PDH) technologies. These technologies rely on continuous and rapid catalyst regeneration to maintain high pr...

According to the recently published QS World University Rankings 2026, ETH Zurich ranks among the world’s ten best universities once again this year. It took the top spot in continental Europe, with o...

The exploitation of shale gas has stimulated the use of on-purpose propane dehydrogenation (PDH) technologies. These technologies rely on continuous and rapid catalyst regeneration to maintain high pr...

While solid–liquid interfaces are ubiquitous, detecting the associated surface sites under ambient conditions remains a grand challenge. Here, we demonstrate an approach to efficiently enhance the NMR...

This study presents a nuclear magnetic resonance-based method to determine local structure and bonding of Pt single-atom catalysts.

This study presents a nuclear magnetic resonance-based method to determine local structure and bonding of Pt single-atom catalysts.

This study presents a nuclear magnetic resonance-based method to determine local structure and bonding of Pt single-atom catalysts.