Leave No Photon Behind: Artificial Intelligence in Multiscale Physics of Photocatalyst and Photoreactor Design.

Although solar fuels photocatalysis offers the promise of converting carbon dioxide directly with sunlight as commercially scalable solutions have remained elusive over the past few decades, despite significant advancements in photocatalysis band-gap engineering and atomic site activity. The primary challenge lies not in the discovery of new catalyst materials, which are abundant, but in overcoming the bottlenecks related to material-photoreactor synergy. These factors include achieving photogeneration and charge-carrier recombination at reactive sites, utilizing high mass transfer efficiency supports, maximizing solar collection, and achieving uniform light distribution within a reactor. Addressing this multi-dimensional problem necessitates harnessing machine learning techniques to analyze real-world data from photoreactors and material properties. In this perspective, the challenges are outlined associated with each bottleneck factor, review relevant data analysis studies, and assess the requirements for developing a comprehensive solution that can unlock the full potential of solar fuels photocatalysis technology. Physics-informed machine learning (or Physics Neural Networks) may be the key to advancing this important area from disparate data towards optimal reactor solutions.

New black indium oxide-tandem photothermal CO2-H2 methanol selective catalyst.

It has long been known that the thermal catalyst Cu/ZnO/Al2O3(CZA) can enable remarkable catalytic performance towards CO2 hydrogenation for the reverse water-gas shift (RWGS) and methanol synthesis reactions. However, owing to the direct competition between these reactions, high pressure and high hydrogen concentration (≥75%) are required to shift the thermodynamic equilibrium towards methanol synthesis. Herein, a new black indium oxide with photothermal catalytic activity is successfully prepared, and it facilitates a tandem synthesis of methanol at a low hydrogen concentration (50%) and ambient pressure by directly using by-product CO as feedstock. The methanol selectivities achieve 33.24% and 49.23% at low and high hydrogen concentrations, respectively.

Solar Urea: Towards a Sustainable Fertilizer Industry.

Urea, an agricultural fertilizer, nourishes humanity. The century-old Bosch-Meiser process provides the world's urea. It is multi-step, consumes enormous amounts of non-renewable energy, and has a large CO2 footprint. Thus, developing an eco-friendly synthesis for urea is a priority. Herein we report a single-step Pd/LTA-3A catalyzed synthesis of urea from CO2 and NH3 under ambient conditions powered solely by solar energy. Pd nanoparticles serve the dual function of catalyzing the dissociation of NH3 and providing the photothermal driving force for urea formation, while the absorption capacity of LTA-3A removes by-product H2 O to shift the equilibrium towards urea production. The solar urea conversion rate from NH3 and CO2 is 87 µmol g-1 h-1 . This advance represents a first step towards the use of solar energy in urea production. It provides insights into green fertilizer production, and inspires the vision of sustainable, modular plants for distributed production of urea on farms.

CO2 Footprint of Thermal Versus Photothermal CO2 Catalysis.

Transformation of CO2 into value-added products via photothermal catalysis has become an increasingly popular route to help ameliorate the energy and environmental crisis derived from the continuing use of fossil fuels, as it can integrate light into well-established thermocatalysis processes. The question however remains whether negative CO2 emission could be achieved through photothermal catalytic reactions performed in facilities driven by electricity mainly derived from fossil energy. Herein, we propose universal equations that describe net CO2 emissions generated from operating thermocatalysis and photothermal reverse water-gas shift (RWGS) and Sabatier processes for batch and flow reactors. With these reactions as archetype model systems, the factors that will determine the final amount of effluent CO2 can be determined. The results of this study could provide useful guidelines for the future development of photothermal catalytic systems for CO2 reduction.

Shining light on CO2: from materials discovery to photocatalyst, photoreactor and process engineering.

Heterogeneous catalysis, a process in which the reaction of gaseous or liquid chemical reagents is facilitated at the surface of a solid material, is responsible for the majority of industrial-scale chemical and fuel production reactions. The energy required to drive these reactions has historically been derived from the combustion of non-renewable fossil fuels and carries an unavoidably large carbon footprint. More recently, the development of environmentally responsible and sustainable chemical industries is increasingly motivated by greenhouse gas-induced climate change, thus creating demand for eco-friendly heterogeneous catalytic processes. This includes innovative approaches enabled by renewable forms of energy, such as the electrification of chemical and petrochemical processes, utilization of CO2 as a feedstock and the incorporation of light into catalytic reactions. Herein we review the conversion of solar energy to chemical energy using CO2, and describe how the photophysical and photochemical properties of nanostructured metal oxide photocatalysts have been engineered to efficiently incorporate light into heterogeneous gas-solid CO2 hydrogenation reactions. Realizing high photonic and energy efficiencies in these systems has demanded innovation in not only photocatalyst engineering, but also photoreactor and process engineering. Rather than exclusively providing an in-depth discussion of the chemistry and science within each individual study, this Tutorial Review highlights the multidisciplinary character of photocatalysis studies by covering the four essential components of a typical research work in this field (materials engineering, theoretical modelling, reactor engineering and process development) via case studies of the archetypal indium oxide catalyst materials. Through advances in these four components, progress has been made towards the ultimate goal of industrializing the production of CO2-derived chemicals and fuels.

Hybrid Photo- and Thermal Catalyst System for Continuous CO2 Reduction.

Heterogeneous thermal catalytic processes are vital for industrial production of fuels, fertilizers, and other chemicals necessary for sustaining human life. However, these processes are highly energy-intensive, requiring a vast consumption of fossil fuels. An emerging class of heterogeneous catalysts that are thermally driven but also exhibit a photochemically enhanced rate can potentially reduce process energy intensity by partially substituting conventional heat (where fossil fuels are needed) with solar energy. Such catalyst systems have yet to be practically utilized. Here, we demonstrate a compact electrically heated photo- and thermal annular reactor module to reduce CO2 to CO, via the reverse water gas shift reaction. A first-principles-based design approach was taken in developing a SiO2 on an Al photo- and thermal catalyst system for the model photo- and thermal indium oxide hydroxide (In2O3-x(OH)y) catalysts. A 5-fold light enhancement in the CO production rate and over 70 h of stable CO production were achieved. This represents the highest light enhancement effect reported for this model photocatalyst to date. The reactor presented herein allows continuous operation and a significant reduction of 31% in heater power consumption when provided with an additional 2 suns of irradiation, demonstrating the strong photo- and thermal-harvesting performances of the catalyst system developed in this work.

Towards Solar Methanol: Past, Present, and Future.

This work aims to provide an overview of producing value-added products affordably and sustainably from greenhouse gases (GHGs). Methanol (MeOH) is one such product, and is one of the most widely used chemicals, employed as a feedstock for ≈30% of industrial chemicals. The starting materials are analogous to those feeding natural processes: water, CO2, and light. Innovative technologies from this effort have global significance, as they allow GHG recycling, while providing society with a renewable carbon feedstock. Light, in the form of solar energy, assists the production process in some capacity. Various solar strategies of continually increasing technology readiness levels are compared to the commercial MeOH process, which uses a syngas feed derived from natural gas. These strategies include several key technologies, including solar-thermochemical, photochemical, and photovoltaic-electrochemical. Other solar-assisted technologies that are not yet commercial-ready are also discussed. The commercial-ready technologies are compared using a technoeconomic analysis, and the scalability of solar reactors is also discussed in the context of light-incorporating catalyst architectures and designs. Finally, how MeOH compares against other prospective products is briefly discussed, as well as the viability of the most promising solar MeOH strategy in an international context.