Terminology, relative photonic efficiencies and quantum yields in heterogeneous photocatalysis. Part I: Suggested protocol

The term photocatalysis is one amongst several in a quagmire of labels used to describe a photon-driven catalytic process; a simple description of photocatalysis is proposed herein. Other labels such as quantum yield and/or quantum efficiency used in solid/liquid and solid/gas hetero-geneous photocatalytic systems to express process efficiencies have come to refer (incorrectly) to the ratio of the rate of a given event to the rate of incident photons impinging on the reactor walls and typically for broadband radiation. There is no accord on the expression for process efficiency. At times quantum yield is defined; often, it is ill-defined and more frequently how it was assessed is not described. This has led to much confusion in the literature, not only because of its different meaning from homogeneous photochemistry, but also because the description of photon efficiency precludes comparison of results from different laboratories owing to variations in light sources, reactor geometries, and overall experimental conditions. The previously reported quantum yields are in fact apparent quantum yields, i.e. lower limits of the true quantum yields. We address this issue and argue that any reference to quantum yields or quantum efficiencies in a heterogeneous medium is inadvisable until the number of photons absorbed by the light harvester (the photocatalyst) is known. A practical and simple alternative is proposed for general use and in particular for processes employing complex reactor geometries: the concept of relative photonic efficiency (xr) is useful to compare process efficiencies using a given photocatalyst material and a given standard test molecule. A quantum yield can subsequently be calculated since f= xrfphenol, where fphenol denotes the quantum yield for the photocatalyzed oxidative transformation of phenol used as the standard secondary actinometer and Degussa P-25 TiO2 as the standard photocatalyst. For heterogeneous suspensions (only), an additional method to determine quantum yields f is also proposed.