Abstract
Conjugated polymers are an emerging class of photocatalysts for hydrogen production where the large breadth of potential synthetic diversity presents both an opportunity and a challenge. Here, we integrate robotic experimentation with high-throughput computation to navigate the available structure–property space. A total of 6354 co-polymers was considered computationally, followed by the synthesis and photocatalytic characterization of a sub-library of more than 170 co-polymers. This led to the discovery of new polymers with sacrificial hydrogen evolution rates (HERs) of more than 6 mmol g–1 h–1. The variation in HER across the library does not correlate strongly with any single physical property, but a machine-learning model involving four separate properties can successfully describe up to 68% of the variation in the HER data between the different polymers. The four variables used in the model were the predicted electron affinity, the predicted ionization potential, the optical gap, and the dispersibility of the polymer particles in solution, as measured by optical transmittance.
Highlights
Hydrogen is an energy carrier that could be a sustainable alternative to fossil fuels in the future.[1]
The subsequent demonstration of photocatalytic water splitting by carbon nitride[9] in 2009 inspired a large number of studies, resulting in materials with high activities for sacrificial half-reactions, as well as reports of overall water splitting.[10−12] Various subclasses of organic photocatalysts have been studied for water splitting, including conjugated microporous polymers (CMPs),[13−20] covalent triazine-based frameworks (CTFs),[21−27] covalent organic frameworks (COFs),[28−31] and linear conjugated polymers.[14,32−37]
In terms of experimentally measured properties, the only property that we found with significant correlation with hydrogen evolution rates (HERs), besides absorption onset, was the light transmittance for a sample of the polymer dispersed in the TEA/MeOH/water photocatalysis mixture (Figure 2d)
Summary
Hydrogen is an energy carrier that could be a sustainable alternative to fossil fuels in the future.[1]. Only a tiny fraction of the possible chemical space for polymer photocatalysts has been explored.[17,38] An alternative approach would be the high-throughput screening of many diverse co-polymers To this end, we developed a set of high-throughput techniques that integrate both experiment and computation, allowing the investigation of a large number of potential co-polymer photocatalysts. Other diboronic acid esters were investigated using a smaller set of dibromide compounds selected from the first screen, giving 76 copolymers By using this tiered computational−experimental strategy, the number of materials that we explored in this study significantly exceeds the total number of conjugated polymer photocatalysts described in the literature so far. Article techniques to test the predictability of HER based on a set of simple, measurable, and/or calculable properties
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