Catalysis is at the core of chemistry and has been essential to make all the goods surrounding us, including fuels, coatings, plastics and other functional materials. In the near future, catalysis will also be an essential tool in making the shift from a fossil-fuel-based to a more renewable and circular society. To make this reality, we have to better understand the fundamental concept of the active site in catalysis. Here, we discuss the physical meaning — and deduce the validity and, therefore, usefulness — of some common approaches in heterogeneous catalysis, such as linking catalyst activity to a ‘turnover frequency’ and explaining catalytic performance in terms of ‘structure sensitivity’ or ‘structure insensitivity’. Catalytic concepts from the fields of enzymatic and homogeneous catalysis are compared, ultimately realizing that the struggle that one encounters in defining the active site in most solid catalysts is likely the one we must overcome to reach our end goal: tailoring the precise functioning of the active sites with respect to many different parameters to satisfy our ever-growing needs. This article ends with an outlook of what may become feasible within the not-too-distant future with modern experimental and theoretical tools at hand.
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B.M.W. acknowledges financial support from the Netherlands Organization for Scientific Research (NWO) in the frame of a Gravitation programme (the Netherlands Center for Multiscale Catalytic Energy Conversion (MCEC), www.mcec-researchcenter.nl), as well as from the Advanced Research Center (ARC) Chemical Buildings Blocks Consortium (CBBC), a public–private research consortium in the Netherlands (www.arc-cbbc.nl). C.V. acknowledges support from a Niels Stensen Fellowship and a VATAT fellowship.
The authors declare no competing interests.
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- Turnover frequency
The turnover frequency is defined as the turnover unit per time. For most industrial applications, the turnover frequency is 10−3–102.
- Structure sensitivity
A reaction in which not all surface sites have the same activity. The surface-normalized activity changes with nanoparticle size for structure-sensitive reactions.
- Turnover number
In enzymology, the maximum number of chemical conversions of substrate molecule that a single catalytic site will execute for a given concentration. In organometallic catalysis, the number of moles of substrate that a mole of catalyst can convert before being deactivated.
- Taylor ratio
The fraction of the catalyst surface that is catalytically active.
- In situ spectroscopy
In situ spectroscopy entails spectroscopic investigation at one or more catalytic conditions (T, p, reactants).
- Operando spectroscopy
Operando spectroscopy studies the reaction while it takes place and is accompanied by the quantification of the reaction products, thereby allowing the direct correlation between structure and performance.
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Vogt, C., Weckhuysen, B.M. The concept of active site in heterogeneous catalysis. Nat Rev Chem 6, 89–111 (2022). https://doi.org/10.1038/s41570-021-00340-y
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