Periodic Reporting for period 1 - SolarCar (Palladium anchored Halide Perovskites for Solar-driven Diphenyl Carbonate Synthesis)
Okres sprawozdawczy: 2023-06-01 do 2025-05-31
As the world faces rising challenges from climate change and plastic pollution, science is searching for sustainable ways to produce everyday materials using renewable energy and environmentally friendly processes. This project responded to that challenge by developing a new solar-powered method to create diphenyl carbonate (DPC), a key building block in the production of polycarbonate plastics, commonly used in electronics, lenses, and medical devices. Traditionally, DPC is produced using toxic chemicals like phosgene, which poses health and environmental risks. This project instead explored an innovative and greener route: using carbon dioxide (CO2) and phenol, a common industrial feedstock, to produce DPC under solar light. By converting waste CO2 into valuable materials, the project aligned with Europe’s sustainability goals and circular economy strategies. The scientific goal was to design new photocatalytic materials that can perform two separate chemical reactions at once: reducing CO2 to carbon monoxide (CO*) and oxidizing phenol to phenoxy radicals (PhO•). These reactive intermediates are then coupled together to form DPC.
In this project, we aimed at two main objectives:
1. Engineering halide perovskites (HPs) with tailored band structures and controlled surface defects to anchor palladium (Pd) clusters or single atoms, creating porous hybrid materials with enhanced sunlight absorption and photocatalytic activity.
2. Demonstrating solar-mediated formation of key intermediates, including phenoxy radicals (PhO•) and carbon monoxide (CO*) from phenol oxidation and CO2 reduction, enabling tandem diphenyl carbonate (DPC) synthesis.
3. Uncovering the reaction mechanism through advanced spectroscopic tools and control experiments, identifying intermediate species and charge-transfer pathways to provide insights into the photocatalytic transformation reactions.
The innovation of this work lies not only in developing a cleaner, safer pathway for DPC production, but also in pioneering a new class of photocatalytic materials, single-atom catalyst (SAC) decorated halide perovskites (Figure 1). This unexplored combination has great potential in solar chemical synthesis and could be extended to other reactions. By bridging material science, green chemistry, and solar energy conversion, the project offers a blueprint for replacing fossil-fuel-based production processes with cleaner, sunlight-powered alternatives advancing both scientific understanding and sustainability goals.
In this project, we aimed at two main objectives:
1. Engineering halide perovskites (HPs) with tailored band structures and controlled surface defects to anchor palladium (Pd) clusters or single atoms, creating porous hybrid materials with enhanced sunlight absorption and photocatalytic activity.
2. Demonstrating solar-mediated formation of key intermediates, including phenoxy radicals (PhO•) and carbon monoxide (CO*) from phenol oxidation and CO2 reduction, enabling tandem diphenyl carbonate (DPC) synthesis.
3. Uncovering the reaction mechanism through advanced spectroscopic tools and control experiments, identifying intermediate species and charge-transfer pathways to provide insights into the photocatalytic transformation reactions.
The innovation of this work lies not only in developing a cleaner, safer pathway for DPC production, but also in pioneering a new class of photocatalytic materials, single-atom catalyst (SAC) decorated halide perovskites (Figure 1). This unexplored combination has great potential in solar chemical synthesis and could be extended to other reactions. By bridging material science, green chemistry, and solar energy conversion, the project offers a blueprint for replacing fossil-fuel-based production processes with cleaner, sunlight-powered alternatives advancing both scientific understanding and sustainability goals.
Over the course of this action, we explored the design and development of advanced photocatalytic systems capable of coupling two distinct half-reactions (CO2 reduction and phenol oxidation) into a unified platform for the sustainable synthesis of diphenyl carbonate (DPC). This project centered around halide perovskite (HP) materials, a class of semiconductors traditionally known for optoelectronic applications, and successfully adapted them for use in solar-driven redox catalysis. By engineering their band structures, surface properties, and defect profiles, we created a new family of hybrid perovskite catalysts decorated with palladium single-atom clusters. These systems exhibited the ability to harvest solar energy and mediate selective redox transformations, generating key reactive intermediates such as CO* and phenoxy radicals (PhO•) under mild conditions. The work further established dual-function photocatalysts that enabled tandem reaction pathways, a strategy rarely explored in perovskite-based catalysis. Through in-depth mechanistic studies supported by spectroscopic characterization and redox potential analysis, we gained critical insight into charge transfer dynamics, surface interactions, and reaction pathways. As a result, this action not only demonstrated proof-of-concept for a cleaner DPC production route but also expanded the functional scope of halide perovskites into the realm of green catalysis, opening up new directions for solar-to-chemical energy conversion.
The project achieved the development of a new class of halide perovskite-based photocatalysts decorated with palladium single atoms for diphenyl carbonate (DPC) synthesis. Key intermediates (CO* and PhO•) were successfully generated under visible light, demonstrating a proof-of-concept for coupling two redox half-reactions using sunlight. This approach offers a sustainable alternative to conventional phosgene-based DPC production. To enable future uptake DPC via photocatalytic reaction, further research is needed on catalyst stability, optimizeation of coupled sites, mechanistic understanding, and reaction scaling. Industrial collaboration and regulatory alignment will also be important for translating this innovation into commercial applications.