Key Takeaways & Executive Findings
- •• • PoTA3 achieves an apparent quantum yield (AQY) of 8.3% under blue light irradiation, with an initial hydrogen evolution rate of 485 mmol g−1 h−1 and a turnover number (TON) of 27,858, demonstrating superior performance for photocatalytic hydrogen production. • • Under white light, PoTA1 and PoTA3 exhibit AQY values of 5.5% and 6.8%, respectively, outperforming the benchmark YD2-o-C8 (AQY = 4.07%) under identical conditions, indicating enhanced broad-spectrum light utilization. • • The dual anchoring groups (4-ethynylbenzoic acid, 3-ethynylbenzoic acid, or 5-ethynylthiophene-2-carboxylic acid) and long-chain alkyloxy substituents suppress charge recombination and reduce aggregation on TiO2 surfaces, improving photocatalytic stability and efficiency. • • The 5-ethynylthiophene-2-carboxylic acid moiety in PoTA3 induces a redshifted and broadened absorption profile, enabling superior solar spectrum utilization and contributing to the highest hydrogen evolution activity among the series.
Abstract
A new generation of porphyrin-based photosensitizers (PoTA1–PoTA3) was developed for photocatalytic hydrogen evolution (PHE). Each photosensitizer features dual anchoring groups—4-ethynylbenzoic acid, 3-ethynylbenzoic acid, or 5-ethynylthiophene-2-carboxylic acid—at the meso-position of the porphyrin macrocycle, along with long-chain alkyloxy substituents. This dual-modification strategy suppresses charge recombination and reduces aggregation on TiO2 surfaces. PoTA3, containing the 5-ethynylthiophene-2-carboxylic acid moiety, exhibits a redshifted and broadened absorption profile, enhancing solar spectrum utilization. Under blue light irradiation, the PoTA3-based system achieves an apparent quantum yield (AQY) of 8.3%, an initial hydrogen evolution rate of 485 mmol g−1 h−1, and a turnover number (TON) of 27,858 in aqueous media, substantially outperforming PoTA1 and PoTA2. Under white light, PoTA1 and PoTA3 achieve AQY values of 5.5% and 6.8%, respectively, surpassing the benchmark YD2-o-C8 (AQY = 4.07%). The synergistic effects of enhanced light harvesting, minimized aggregation, and optimized HOMO/LUMO electron density distributions contribute to high efficiency and robust operational stability. These findings establish a flexible molecular engineering platform for next-generation solar-to-hydrogen conversion systems.
1. Introduction
Global energy demand and environmental concerns necessitate sustainable hydrogen production. Conventional methods, such as fossil fuel reforming, are finite and emit carbon dioxide. Photocatalytic water splitting using solar energy offers a clean alternative, but requires efficient and affordable photocatalysts. Porphyrins, as chlorophyll analogs, are promising due to their visible-light absorption and photostability, yet their performance is often limited by charge recombination and aggregation on semiconductor surfaces.
This work addresses these bottlenecks through molecular engineering of porphyrin photosensitizers with dual anchoring groups and alkyloxy substituents. The dual anchoring groups enhance binding to TiO2, while the alkyloxy chains reduce aggregation, collectively improving charge separation and light harvesting. The introduction of a thiophene-based anchoring group in PoTA3 further extends absorption into the red region, maximizing solar spectrum utilization. These modifications lead to record AQY and hydrogen evolution rates, demonstrating a viable strategy for next-generation photocatalytic systems.
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Yudong Wen, Cheuk-Lam Ho, Yan Yi Kwok (2026). Molecularly engineered porphyrin photosensitizers featuring multi-anchoring and alkoxy modifications for robust photocatalytic hydrogen production. SCIENCE CHINA Materials. https://doi.org/10.1007/s40843-025-3715-5
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Frequently Asked Questions
What is the long-term operational stability of PoTA3 under continuous irradiation, and are there any degradation pathways observed?
The paper reports a turnover number (TON) of 27,858 for PoTA3 under blue light, indicating high durability. However, specific long-term stability data beyond initial rates are not provided. The dual anchoring and alkyloxy groups are designed to reduce aggregation and charge recombination, which likely contribute to stability, but further studies on photodegradation mechanisms are needed.
How does the performance of PoTA3 compare to state-of-the-art noble metal-based photosensitizers in terms of cost and efficiency?
PoTA3 is a noble metal-free photosensitizer, offering cost advantages over platinum-based systems. Its AQY of 8.3% under blue light and 6.8% under white light is competitive with many reported systems. However, direct comparison with noble metal-based systems requires identical conditions; the paper benchmarks against YD2-o-C8, a known porphyrin sensitizer, and PoTA3 outperforms it.
What is the scalability potential of the synthesis route for PoTA1–PoTA3?
The synthesis involves standard porphyrin functionalization steps, which are generally scalable. The use of common reagents and moderate conditions suggests feasibility for scale-up, but detailed yield and cost analysis are not provided. Industrial adoption would require optimization of synthetic steps and purification processes.
Are there any limitations in the photocatalytic system, such as dependence on sacrificial electron donors or pH conditions?
The paper mentions aqueous media, but specific details on sacrificial donors or pH are not given. Typically, such systems use sacrificial agents like triethanolamine or ascorbic acid. The performance metrics are reported under specific conditions, and further optimization for practical applications would require addressing these dependencies.
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