Funding Agencies and Institutions
Electrocatalytic Synthesis of Ammonia from Nitrate Reduction: The Role of Copper and Its Oxides as Efficient Catalysts
FAPESP SPRINT (22/14169-6): The electrocatalytic synthesis of ammonia from the reduction of nitrate ions has emerged as a promising technology to replace the energy-intensive Haber-Bosch process. Ammonia can be synthetized electrochemically with interesting efficiencies and formation rate values, and when coupled with a sustainable energy matrix, a “green” seal can be obtained. Among several metals, Cu has shown the fastest rate-determining step of nitrate to nitrite, the highest electrocatalytic reduction kinetics and weak hydrogen evolution ability in low overpotentials. When combining it with Cu oxides, an outstanding activity and selectivity is observed for the formation of ammonia. Atomistic calculations have reported the stabilization of adsorbed NOH intermediate as the main responsible for the excellent performance to ammonia production, going through successive reduction steps to hydroxylamine and then ammonia. We propose in this project the electrosynthesis of ammonia from the reduction of nitrate ions on Cu-based oxides as electrocatalysts with different surface and bulk compositions. The idea relies on the better understanding of why copper and its oxides seem to catalyze the reaction effectively. For this aim, we intend to apply in situ (FTIR and Raman) and on line (DEMS and GC) techniques coupled to the electrochemical cell in order to monitor the molecular aspects of the reaction and in combination with the physical characterization of the catalyst (TEM, XPS, XRD, AFM, etc), draw a close correlation between the material properties with the electrocatalysis of the nitrate reduction reaction. The synergic combination of the expertise of both proponents of this project will facilitate a deeper mechanistic investigation of energy conversion reactions, aiming the development of more efficient and selective catalysts. As an additional outcome, a long-term joint cooperation will be strengthened.
Tandem Dissipative Electrodes Applied in the Reduction of Carbon Dioxide to the Formation of C2+ Products
FAPESP Regular Program (21/08868-6): This project proposes a bio-inspired synthesis route of dissipative materials, created in conditions away from the thermodynamic equilibrium, as paradigmatic catalysts for the production of dense energy carriers from the electrochemical reduction of carbon dioxide. The materials will be synthesized at the solid/liquid interface by nonlinear electrodeposition reactions, aiming at a higher level of complexity and emerging properties which are not obtained by usual synthetic methods. Emphasis will be given to the design and control of a microscale segregated phase structure, between copper and gold, silver or zinc, for example, in order to induce a catalytic reaction in tandem (or cascade). In this strategy, carbon monoxide will be produced in the guest metal and sequentially dimerized at active copper sites, forming molecules with multiple carbon atoms. The electronic and structural properties of the dissipative material will be evaluated by X-ray spectroscopies and advanced microscopy techniques, being intrinsically correlated with product distribution. It is expected to create new catalysts, with easy scaling up, that surpass the state-of-the-art benchmarks for electrochemical reduction of carbon dioxide.
(Photo)Electrochemical Production of Value-Added Products from the Conversion of CO2 and Glycerol
CNPq Universal (402481/2021-6): The continuous growth in energy demand and the effects caused by global warming have stimulated the development of sustainable energy conversion and storage systems. In Brazil, there are optimal conditions for the use of solar and/or wind energy in a large part of the territory. These intermittent sources of energy provide green electrons that can be used to carry out different types of electrochemical reactions. In fact, the theme fits into the priority areas of research defined by the MCTI. CO2 is a gas generated during the burning of fossil fuels in many industrial processes and mostly discarded into the atmosphere, which contributes to global warming. Glycerol is a by-product of obtaining biodiesel, a well-established industry in Brazil. Unfortunately, there is now an accumulation of glycerol as its generation is greater than the demand. Thus, in this project, we propose the development of materials to use CO2 and glycerol to generate value-added products through electrochemical processes. The development of catalysts with optimized structure and composition is essential to carry out these reactions efficiently (fast and with high yields) and selectively (obtaining the desired product). The rational preparation of these materials is not possible without knowledge of the microscopic processes that take place at the electrode-solution interface. Thus, in this project, in addition to the synthesis, we propose systematic studies using in situ characterization techniques in order to understand how these reactions occur in the following materials: i) mixture of Cu/Au nanoalloys and Cu nanoparticles aiming at the Tandem effect (for reduction of CO2) and ii) semiconductor oxides, perovskite oxides and nanoparticles with low content of noble metals (for the electrooxidation of glycerol).
Ellipso-microscopy for Surface Imaging
FAPESP Multiuser Equipament (17/00089-2): Microscopy techniques with spatiotemporal resolution are essential for the understanding of the spontaneous formation of self-organized structures in the electrochemical interface. The extraction of surface images by ellipsometric microscopy (ellipso-microscopy for surface imaging, EMSI) in real time is distinguished to be a non-destructive and very sensitive technique. Along with the spectroscopic module, it is possible to measure accurate values of thickness, refraction index and extinction coefficient of thin films formed on the metallic surface with lateral and depth precision in micro and nanoscale, respectively. This multi-user equipment, associated with the project Young Investigator of FAPESP, process: 2016/01817-9, aims to contribute to a systemic investigation of the physical chemistry of the surface reactions with spatiotemporal resolution, revealing important emerging properties related to the self-organizing process.
Dense Energy Carriers – Center for Innovation on New Energies
FAPESP Research Centers in Engineering Program (17/11986-5): The Dense Energy Carrier Division will consolidate expertise in materials processing, advanced characterization and physics of semiconductors devices of LNNano/CNPEM with that of Universidade Estadual de Campinas (UNICAMP), Universidade Federal do ABC (UFABC) and Universidade Federal de São Carlos (UFSCar) in electrochemistry and photoelectrochemestry to develop state-of-the-art research in the field of solar driven routes to synthesize molecules via photoelectrochemical approach. Molecules offer the highest energy densities when compared to any form of electricity storage and are therefore referred to as Dense Energy Carriers (DEC). However, most of molecules used as fuel nowadays are processed by non-renewable and non-sustainable technologies or by bio-fuels technologies. Certainly, solar driven routes to synthesize molecules based on the photoelectrochemical approach are alternative ways to be explored in order to produce liquid fuel in a sustainable and “green” way. Keeping this in mind, the focus of this research division is the development of efficient solar driven routes to synthesize relevant product molecules from molecules that are widely available in the environment. In this way, we intend to explore the following routes to obtain high efficiency materials regarding the solar energy conversion into molecules: i) Understand materials and manufacturing challenges (e.g. thin films, inkjet printing, coatings, and atomic layer deposition process) ii) Development of novel materials and nanostructured materials (e.g. electrodes, and structured catalyst) for photoelectrochemical conversion iii) Production of H2, alcohols or hydrocarbons from CO2 and water using electrochemical and photoelectrochemical conversion In terms of technology readiness level (TRL), i.e., in terms of technology maturity, most of our research projects are located in a level classified from 1 to 3. We intend to upgrade projects that reach TRL level 3 into TRL level 4 in the first 5 years of financial support. This will be the more important task of the Technology Transfer Coordinator (TTC), in the Innovation division of our research center. The main proposal is that the Innovation Division acts as a bridge between academic research and industrial research. Innovation Division will seek to fill the gap (in terms of TRL) between academic research and industrial development. The Innovation Division will promote also workshops to demonstrate the technologies under development in the research division as well as, workshops to discuss the implementation of public policy for alternative and renewable energy. Other important point of our proposal are the activities that the Education and Dissemination of Knowledge division will implement during the duration of the project. Basically, two lines of action will be developed under this proposal: 1. prioritizing the theme of renewable energy, mainly related to solar driven routes to synthesize liquid fuels; 2. developing new products and specific projects. The planned actions will target different segments of the public, ranging from communication among the New Energy Research Center (NERC) researchers themselves to efforts directed to students (and teachers) from primary and secondary school, including also communication via the mainstream media (through press advisory activities) and activities aimed at the public at the beginning of their university education; these actions will also deal, concomitantly, with the elementary physical and chemical processes associated with the topics addressed and the more advanced applications to be developed during the investigations, as well as with cross-cutting issues such as, in particular, environmental issues.
4. Spatiotemporal Resolution of Metal Oxides on Polycrystalline Surfaces
CNPq Universal (405235/2018-6)
3. Engineering Self-organized Nanostructured Materials by Nonlinear Chemical Dynamics Control
FAPESP SPRINT (18/21619-2)
2. Career Start Assistance in UNICAMP
Dean of Research (2709/18)
1. Design and Control of Self-organized Electrochemical Patterns
FAPESP Young Investigator Program (16/01817-9)