Solving the structure of carbon nitrides has been a long-standing challenge due to the low crystallinity and complex structures observed within this class of earth-abundant photocatalysts. Herein, we report on two-dimensional layered potassium poly(heptazine imide) (K-PHI) and its proton-exchanged counterpart (H-PHI), obtained by ionothermal synthesis using a molecular precursor route. We present a comprehensive analysis of the in-plane and three-dimensional structure of PHI. Transmission electron microscopy and solid-state NMR spectroscopy, supported by quantum-chemical calculations, suggest a planar, imide-bridged heptazine backbone with trigonal symmetry in both K-PHI and H-PHI, whereas pair distribution function analyses and X-ray powder diffraction using recursive-like simulations of planar defects point to a structure-directing function of the pore content. While the out-of-plane structure of K-PHI exhibits a unidirectional layer offset, mediated by hydrated potassium ions, H-PHI is characterized by a high degree of stacking faults due to the weaker structure directing influence of pore water. Structure–property relationships in PHI reveal that a loss of in-plane coherence, materializing in smaller lateral platelet dimensions and increased terminal cyanamide groups, correlates with improved photocatalytic performance. Size-optimized H-PHI is highly active toward photocatalytic hydrogen evolution, with a rate of 3363 μmol/gh H2 placing it on par with the most active carbon nitrides. K- and H-PHI adopt a uniquely long-lived photoreduced polaronic state in which light-induced electrons are stored for more than 6 h in the dark and released upon addition of a Pt cocatalyst. This work highlights the importance of structure–property relationships in carbon nitrides for the rational design of highly active hydrogen evolution photocatalysts.

Solar-to-chemical energy conversion for the generation of high energy chemicals is one of the most viable, non-intermittent solutions to the present-day lookout for sustainable energy resources. Recently, organic polymeric photocatalysts have garnered significant attention in this field of research, which has long been dominated by inorganic semiconductors. Revisiting the lessons learnt from the latter, we reevaluate the fundamental concepts of photocatalysis in the context of the different classes of polymeric photocatalysts known to date, ranging from carbon nitrides and conjugated polymers, to covalent triazine frameworks and covalent organic frameworks. We then analyze the photophysical and physicochemical concepts that govern the photocatalytic performance of these materials, and thereby derive pertinent design principles and possible future research directions in this emerging field of "soft photocatalysis".

Graphitic carbon nitrides have emerged as an earth-abundant family of polymeric materials for solar energy conversion. Herein, a 2D cyanamide-functionalized polyheptazine imide (NCN-PHI) is reported, which for the first time enables the synergistic coupling of two key functions of energy conversion within one single material: light harvesting and electrical energy storage. Photo-electrochemical measurements in aqueous electrolytes reveal the underlying mechanism of this "solar battery" material: the charge storage in NCN-PHI is based on the photoreduction of the carbon nitride backbone and charge compensation is realized by adsorption of alkali metal ions within the NCN-PHI layers and at the solution interface. The photoreduced carbon nitride can thus be described as a battery anode operating as a pseudocapacitor, which can store light-induced charge in the form of long-lived, "trapped" electrons for hours. Importantly, the potential window of this process is not limited by the water reduction reaction due to the high intrinsic overpotential of carbon nitrides for hydrogen evolution, potentially enabling new applications for aqueous batteries. Thus, the feasibility of light-induced electrical energy storage and release on demand by a one-component light-charged battery anode is demonstrated, which provides a sustainable solution to overcome the intermittency of solar radiation.