TY - JOUR A1 - Mohan, Abhinav A1 - Ulmer, Ulrich A1 - Hurtado, Lourdes A1 - Loh, Joel A1 - Li, Young Feng A1 - Tountas, Athanasios A. A1 - Krevert, Carola A1 - Chan, Chakyu A1 - Liang, Yilei A1 - Brodersen, Peter A1 - Sain, Mohini M. A1 - Ozin, Geoffrey A. T1 - Hybrid Photo- and Thermal Catalyst System for Continuous CO2 Reduction JF - ACS Applied Materials & Interfaces N2 - 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. Y1 - 2020 U6 - https://doi.org/10.1021/acsami.0c06232 SN - 1944-8244 VL - 12 IS - 30 SP - 33613 EP - 33620 PB - American Chemical Society (ACS) ER - TY - JOUR A1 - Dong, Yuchan A1 - Duchesne, Paul A1 - Mohan, Abhinav A1 - Ghuman, Kulbir Kaur A1 - Kant, Paul A1 - Hurtado, Lourdes A1 - Ulmer, Ulrich A1 - Loh, Joel Y. Y. A1 - Tountas, Athanasios A. A1 - Wang, Lu A1 - Ali, Feysal M. A1 - Xia, Meikun A1 - Dittmeyer, Roland A1 - Ozin, Geoffrey A. T1 - Shining light on CO2: from materials discovery to photocatalyst, photoreactor and process engineering JF - Chemical Society Reviews N2 - 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. Y1 - 2020 U6 - https://doi.org/10.1039/D0CS00597E SN - 0306-0012 VL - 49 IS - 16 SP - 5648 EP - 5663 PB - Royal Society of Chemistry (RSC) ER - TY - JOUR A1 - Guo, Jiuli A1 - Duchesne, Paul N. A1 - Wang, Lu A1 - Song, Rui A1 - Xia, Meikun A1 - Ulmer, Ulrich A1 - Sun, Wei A1 - Dong, Yuchan A1 - Loh, Joel Y. Y. A1 - Kherani, Nazir P. A1 - Du, Jimin A1 - Zhu, Baolin A1 - Huang, Weiping A1 - Zhang, Shoumin A1 - Ozin, Geoffrey A. T1 - High-Performance, Scalable, and Low-Cost Copper Hydroxyapatite for Photothermal CO2 Reduction JF - ACS Catalysis Y1 - 2020 U6 - https://doi.org/10.1021/acscatal.0c03806 SN - 2155-5435 VL - 10 IS - 22 SP - 13668 EP - 13681 PB - American Chemical Society (ACS) ER - TY - JOUR A1 - Xia, Meikun A1 - Mao, Chengliang A1 - Gu, Alan A1 - Tountas, Athanasios A. A1 - Qiu, Chenyue A1 - Wood, Thomas E. A1 - Li, Young Feng A1 - Ulmer, Ulrich A1 - Xu, Yangfan A1 - Viasus, Camilo J. A1 - Ye, Jessica A1 - Qian, Chenxi A1 - Ozin, Geoffrey T1 - Solar Urea: Towards a Sustainable Fertilizer Industry JF - Angewandte Chemie N2 - 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 H2O 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. Y1 - 2021 U6 - https://doi.org/10.1002/ange.202110158 SN - 0044-8249 VL - 134 IS - 1 PB - Wiley ER - TY - JOUR A1 - Hurtado, Lourdes A1 - Mohan, Abhinav A1 - Ulmer, Ulrich A1 - Natividad, Reyna A1 - Tountas, Athanasios A. A1 - Sun, Wei A1 - Wang, Lu A1 - Kim, Boeun A1 - Sain, Mohini M. A1 - Ozin, Geoffrey A. T1 - Solar CO2hydrogenation by photocatalytic foams JF - Chemical Engineering Journal N2 - Here we report the enhanced light penetration and mass transfer efficiency of photocatalytic foams to convert CO2 to CO. The viability of utilizing a metallic foam as a model photocatalyst support is used to evaluate the photochemical and thermochemical reverse water gas shift reaction catalyzed by photoactive indium oxide hydroxide nanorods uniformly coated on nickel foams. A light-enhanced CO production rate up to 130% higher than the dark CO production was achieved through enhanced light penetration. A remarkably high thermo- chemical CO production rate of 0.75 mmol gcat 1 h 1 was achieved at 295 ◦C. Whilst several approaches to optimization of photocatalyst morphology at the nanoscale have been successful in extending electron hole-pair lifetime and modifying the site of reactions, these advantages cannot be significantly realized unless microscale to macroscale structuring efforts, that shorten the path length for diffusion of the reactant gas molecule and lengthen photon penetration to these catalytic sites are integrated. The superior catalytic performance of the indium oxide hydroxide nanorods on an optimized coated foam configuration compared to the performance of packed bed and thin film configurations demonstrates the critical importance of using structured supports in scale up of future photocatalytic processes. Y1 - 2022 U6 - https://doi.org/10.1016/j.cej.2022.134864 SN - 1385-8947 VL - 435 PB - Elsevier BV ER -