Considering their superior charge-transfer characteristics, easy tenability of energy levels, and low production cost, organic semiconductors are ideal for photoelectrochemical (PEC) hydrogen production. However, organic-semiconductor-based photoelectrodes have not been extensively explored for PEC water-splitting because of their low stability in water. Herein, we report high-performance and stable organic-semiconductors photoanodes consisting of p-type polymers and n-type non-fullerene materials, which is passivated using nickel foils, GaIn eutectic, and layered double hydroxides as model materials. We achieve a photocurrent density of 15.1 mA cm−2 at 1.23 V vs. reversible hydrogen electrode (RHE) with an onset potential of 0.55 V vs. RHE and a record high half-cell solar-to-hydrogen conversion efficiency of 4.33% under AM 1.5 G solar simulated light. After conducting the stability test at 1.3 V vs. RHE for 10 h, 90% of the initial photocurrent density are retained, whereas the photoactive layer without passivation lost its activity within a few minutes.

The importance of hydrogen peroxide (H 2 O 2 ) continues to grow globally. Deriving the oxygen reduction reaction (ORR) toward the 2epathway to form H 2 O 2 is crucial for high H 2 O 2 productivity. However, most selective electrocatalysts following the 2epathway comprise carbon-containing organic materials with intrinsically low stability, thereby limiting their commercial applicability. Herein, layered double hydroxides (LDHs) are used as inorganic matrices for the first time. The LDH catalyst developed herein exhibits near-100% 2e -ORR selectivity and stably produces H 2 O 2 with a concentration of ≈108.2 mm cm -2 photoanode in 24 h in a two-compartment system (with a photoanode) with a solar-to-chemical conversion efficiency of ≈3.24%, the highest among all reported systems. Density functional theory calculations show that 2e -ORR selectivity is promoted by atomically dispersed cobalt atoms in (012) planes of the LDH catalyst, while a free energy gap between the * O and OOHstates is an important factor.

Highly efficient electrocatalysts for the oxygen evolution reaction (OER) in neutral electrolytes are indispensable for practical electrochemical and photoelectrochemical water splitting technologies. However, there is a lack of good, neutral OER electrocatalysts because of the poor stability when H+ accumulates during the OER and slow OER kinetics at neutral pH. Herein, we report Ir species nanocluster-anchored, Co/Fe-layered double hydroxide (LDH) nanostructures in which the crystalline nature of LDH-restrained corrosion associated with H+ and the Ir species dramatically enhanced the OEC kinetics at neutral pH. The optimized OER electrocatalyst demonstrated a low overpotential of 323 mV (at 10 mA cm–2) and a record low Tafel slope of 42.8 mV dec–1. When it was integrated with an organic semiconductor-based photoanode, we obtained a photocurrent density of 15.2 mA cm–2 at 1.23 V versus reversible hydrogen in neutral electrolyte, which is the highest among all reported photoanodes to our knowledge.

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Organic semiconductor-based photoelectrodes are gaining significant attention in photoelectrochemical (PEC) value-added chemical production systems, which are promising architectures for solar energy harvesting. Organic semiconductors consisting of conjugated carbon–carbon bonds provide several advantages for PEC cells, including improved charge transfer, tunable band positions and band gaps, low cost, and facile fabrication using organic solvents. This review gives an overview of the recent advances in emerging single organic semiconductor-based photoelectrodes for PEC water splitting and the various strategies for enhancing their performance and stability. It highlights the importance of photoelectrodes based on donor–acceptor bulk heterojunction (BHJ) systems for fabricating efficient organic semiconductor-based solar energy-harvesting devices. Furthermore, it evaluates the recent progress in BHJ organic base photoelectrodes for producing highly efficient PEC value-added chemicals, such as hydrogen and hydrogen peroxide. Finally, this review highlights the potential of organic-based photoelectrodes for bias-free solar-to-chemical production, which is the ultimate goal of PEC systems and a step toward achieving reliable commercial technology.