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Green hydrogen is the key to the chemical industry achieving net zero emissions. The chemical industry is responsible for almost 2% of all CO2 emissions, with half of it coming from the production of simple commodity chemicals, such as NH3, H2O2, methanol, and aniline. Despite electrolysis driven by renewable power sources emerging as the most promising way to supply all the green hydrogen required in the production chain of these chemicals, in this review, it is worth noting that the photocatalytic route may be underestimated and can hold a bright future for this topic. In fact, the production of H2 by photocatalysis still faces important challenges in terms of activity, engineering, and economic feasibility. However, photocatalytic systems can be tailored to directly convert sunlight and water (or other renewable proton sources) directly into chemicals, enabling a solar‐to‐chemical strategy. Here, a series of recent examples are presented, demonstrating that photocatalysis can be successfully employed to produce the most important commodity chemicals, especially on NH3, H2O2, and chemicals produced by reduction reactions. The replacement of fossil‐derived H2 in the synthesis of these chemicals can be disruptive, essentially safeguarding the transition of the chemical industry to a low‐carbon economy. [ABSTRACT FROM AUTHOR]

Photochargeable semiconductors enable energy harvesting and storage in a single material. Charges separated upon absorption of photons can accumulate in highly energetic trap states if morphology, size, and chemical composition are appropriately chosen. For example, electrons can survive for several hours if hole scavengers are used to prevent their recombination with photogenerated holes, and their negative charge is balanced by positive counter‐ions. The first database of charge‐storing semiconductors is recently released, containing information from more than 50 publications within the past 40 years. Now, the database has been updated with more than 90 entries from the latest works on the topic. These materials have been largely utilized in the context of "dark photocatalysis", that is, redox reactions enabled by photocharged semiconductors long after cessation of light irradiation. Nevertheless, a variety of further potential applications have not received enough visibility, including memory storage, steel anti‐corrosion, sensors, and micromotors. In this review, the key figures of merit of photocharged semiconductors and the empirical relationships found between them is highlighted. After showing the latest advances in dark photocatalysis, it is discussed how other application fields may benefit from these materials. For each area, promising research directions based on the findings from the database are recommended. [ABSTRACT FROM AUTHOR]

Recently, the missing link between homogeneous and heterogeneous catalysis has been found and it was named single-atom catalysis (SAC). However, the SAC field still faces important challenges, one of which is controlling the bonding/coordination between the single atoms and the support in order to compensate for the increase in surface energy when the particle size is reduced due to atomic dispersion. Excellent candidates to meet this requirement are carbon nitride (CN)-based materials. Metal atoms can be firmly trapped in nitrogen-rich coordination sites in CN materials, which makes them a unique class of hosts for preparing single-atom catalysts (SACs). As one of the most promising two-dimensional supports to stabilize isolated metal atoms, CN materials have been increasingly employed for preparing SACs. Herein, we will cover the most recent advances in single-atoms supported by CN materials. In this review, the most important characterization techniques and the challenges faced in this topic will be discussed, and the commonly employed synthetic methods will be delineated for different CN materials. Finally, the catalytic performance of SACs based on carbon nitrides will be reviewed with a special focus on their photocatalytic applications. In particular, we will prove CN as a non-innocent support. The relationship between single-atoms and carbon nitride supports is two-way, where the single-atoms can change the electronic properties of the CN support, while the electronic features of the CN matrix can tune the catalytic activity of the single sites in photocatalytic reactions. Finally, we highlight the frontiers in the field, including analytical method development, truly controlled synthetic methods, allowing the fine control of loading and multi-element synthesis, and how understanding the two-way exchange behind single-atoms and CN supports can push this topic to the next level. [ABSTRACT FROM AUTHOR]

Green hydrogen is the key to the chemical industry achieving net zero emissions. The chemical industry is responsible for almost 2% of all CO 2 emissions, with half of it coming from the production of simple commodity chemicals, such as NH 3 , H 2 O 2 , methanol, and aniline. Despite electrolysis driven by renewable power sources emerging as the most promising way to supply all the green hydrogen required in the production chain of these chemicals, in this review, it is worth noting that the photocatalytic route may be underestimated and can hold a bright future for this topic. In fact, the production of H 2 by photocatalysis still faces important challenges in terms of activity, engineering, and economic feasibility. However, photocatalytic systems can be tailored to directly convert sunlight and water (or other renewable proton sources) directly into chemicals, enabling a solar-to-chemical strategy. Here, a series of recent examples are presented, demonstrating that photocatalysis can be successfully employed to produce the most important commodity chemicals, especially on NH 3 , H 2 O 2 , and chemicals produced by reduction reactions. The replacement of fossil-derived H 2 in the synthesis of these chemicals can be disruptive, essentially safeguarding the transition of the chemical industry to a low-carbon economy., Competing Interests: The authors declare no conflict of interest., (© 2023 The Authors. Global Challenges published by Wiley‐VCH GmbH.)

Photocatalysis provides a sustainable pathway to produce the consumer chemical H 2 O 2 from atmospheric O 2 via an oxygen reduction reaction (ORR). Such an alternative is attractive to replace the cumbersome traditional anthraquinone method for H 2 O 2 synthesis on a large scale. Carbon nitrides have shown very interesting results as heterogeneous photocatalysts in ORR because their covalent two-dimensional (2D) structure is believed to increase selectivity toward the two-electron process. However, an efficient and scalable application of carbon nitrides for this reaction is far from being achieved. Poly(heptazine imides) (PHIs) are a more powerful subgroup of carbon nitrides whose structure provides high crystallinity and a scaffold to host transition-metal single atoms. Herein, we show that PHIs functionalized with sodium and the recently reported fully protonated PHI exhibit high activity in two-electron ORR under visible light. The latter converted O 2 to up to 1556 mmol L -1 h -1 g -1 H 2 O 2 under 410 nm irradiation using inexpensive but otherwise chemically demanding glycerin as a sacrificial electron donor. We also prove that functionalization with transition metals is not beneficial for H 2 O 2 synthesis, as the metal also catalyzes its decomposition. Transient photoluminescence spectroscopy suggests that H-PHIs exhibit higher activity due to their longer excited-state lifetime. Overall, this work highlights the high photocatalytic activity of the rarely examined fully protonated PHI and represents a step forward in the application of inexpensive covalent materials for photocatalytic H 2 O 2 synthesis.

Plasmonic catalysis in the colloidal phase requires robust surface ligands that prevent particles from aggregation in adverse chemical environments and allow carrier flow from reagents to nanoparticles. This work describes the use of a water-soluble conjugated polymer comprising a thiophene moiety as a surface ligand for gold nanoparticles to create a hybrid system that, under the action of visible light, drives the conversion of the biorelevant NAD + to its highly energetic reduced form NADH. A combination of advanced microscopy techniques and numerical simulations revealed that the robust metal-polymer heterojunction, rich in sulfonate functional groups, directs the interaction of electron-donor molecules with the plasmonic photocatalyst. The tight binding of polymer to the gold surface precludes the need for conventional transition-metal surface cocatalysts, which were previously shown to be essential for photocatalytic NAD + reduction but are known to hinder the optical properties of plasmonic nanocrystals. Moreover, computational studies indicated that the coating polymer fosters a closer interaction between the sacrificial electron-donor triethanolamine and the nanoparticles, thus enhancing the reactivity.