Novel Copper-electrocatalyst architectures for CO2 reduction reaction

Project Coordinator: University of Bucharest  Faculty of Physics,  3NANO-SAE Research Center, University of Bucharest, the largest and most prestigious academic institution, has over 140 years of experience and expertise in education and research, recently receiving the title of “University ”. with the most intense research activity ”. In 2007, a survey by The Times Higher Education Supplement ranked the University of Bucharest in the top 500 most prestigious universities. Organized in Faculties and Departments, it carries out its activities on three study programs, Master’s programs (117) and 21 doctoral schools with 300 supervisors and 3000 doctoral students. 3Nano-SAE Research and Development Center, located in the Faculty of Physics, department with research activities in biosensors, nanoelectronics, fuel cell technology, hydrogen systems, hybrid energy systems, coordinator of the doctoral school and the postdoctoral school Pile de Combustie . and Hydrogen Storage. The infrastructure consists of laboratories: fuel cell testing, hydrogen generation and storage, biofuel cells, hybrid energy systems engineering, material characterization (Charm), Plasma Chemistry, Photoresist, and polymer printing technology (PCPT), advanced chemistry of synthesis and deposition of polymers (APSC). There is an extensive and unique campus within the Faculty of Physics covering methods of synthesis, processing, and characterization of materials such as semiconductors, polymers, nanocomposites. Research interests include conventional and innovative nanomaterials, structures and devices needed in the design of fuel cells, sensors (chemical, electrochemical), plasma polymerization, electrochemical polymerization, supercritical fluids, sol-gel, materialized in a large list of projects / collaborations: 9 international projects and 35 national projects.

Project leader: 

Dr. Adriana Balan, Lector/CSIII, Facultatea de Fizică, Universitatea din București, titlul de Doctor în Fizică obținut în anul 2011.  Este co-fondator al Centrului de Cercetare 3Nano-SAE și coordonează activitatea de cercetare a studenților în cadrul programului de master Surse de Energii Regenerabile și Alternative, în cadrul Facultății de Fizică. Experiență profesională în activitatea de cercetare: materiale compozite polimerice, carbonice cu aplicații în dispozitive electrochimice- pile de combustie, metode de caracterizare materiale- microscopie de forțe atomice, analize termice, electrochimie. Participă în implementare proiectului internațional ”Metode inovative de învățare pentru viitorii specialiști în energii regenerabile” care are ca obiectiv crearea unei platforme educaționale între Universitatea Reykjavik și Universitatea din București și mobilități inter-universitare în vederea formării viitorilor specialiștilor în energie regenerabilă. A fost director sau responsabil de proiect în cinci proiecte de cercetare naționale și a participat în 15 proiecte ca membru în echipă. Este co-autor a patru brevete naționale, a publicat 57 de lucrări ISI, cu peste 500 de citări, indice Hirsh 13 (http://www.researcherid.com/rid/B-7331-2011).

Team Members: 

Cornelia Diac, age: 28, PhD in Physics (2017-2021). Over the Ph.D program I accumulated a rich experience in managing and conducting project activities, being able to undergo research topics of great complexity in the field of electrochemistry and dissolution processes. I gained significant knowledge in electrochemical processes and I learned how to operate a large group of devices, from which relevant to this project: Electrochemical potentiostat/galvanostat, ICP – OES, Raman, UV – Vis Spectroscopy, CHNS Elemental Analyzer, Thermogravimetric analyzer.

Drd. Tom Iacob is a PhD student at the Faculty of Physics of the University of Bucharest were he studies the possibility of CO2 reduction with the help of microorganisms, he holds a MSc from the Faculty of Physics with the thesis title: Bioelectrochemical systems. Elaboration of a working method for redox potential determination of bacteria culture. He worked for more than two years at the Institute of Biology of Romanian Academy at Microbiology department and has experience in monitoring bacteria in bioelectrochemical systems and microbial fuel cells. He also has knowledge in working with UV-vis spectrometers, potentiostats, ICP-oes and Plasma RF generator.

Drd. Bogdan Ciprian Mitrea has been interested in fuel cell technology since his undergraduate studies at the University of Bucharest’s Faculty of Physics. He earned a degree in physics with a thesis on “Determining the Efficiency of Fuel Cells” and went on to earn a master’s degree in “Assembly and Testing of g-C₃N₄ Photoelectrodes”. He is now working to increase the efficiency of photocatalysts in redox reactions in order to explore CO₂ reduction processes using photoelectrochemical cells. Additionally, he is researching possible uses for nanoparticles in plant growth and development. Bogdan gained expertise in the use of electrochemical potentiostats, optical microscopy, UV-visible spectroscopy, semiconductor treatment in O₂ plasma, polymerization in direct current plasma (DC), and thin film deposition by magnetron sputtering.

Dr. Ioan Stamatin, Professor Ph.D, at the Faculty of Physics, University of Bucharest (FF-UB). Areas of expertise: Electrochemical energy converters (Fuel cells, batteries, supercapacitors); Eco-nanotechnologies; Nanomaterials Synthesis; Polymers, biopolymers, bio-nanotechnologies; Rapid Prototyping and energy storage applications (supercapacitors, batteries, sensors); Electrocatalysts based platinum used in fuel cells; Sensors and electrochemical method for different analyte detections; Physico–chemical characterization of materials by spectroscopy (UV-Vis, FT-IR ATR, fluorescence); optical microscopy; ultrasound treatments. He is the founder and leader of 3NanoSAE Research Center, and his main expertise is in material science and characterization. He published 155 scientific papers; Patents indexed in Derwent international data base: 14; He supervised and refereed 28 PhD thesis; Project Leader in 7 projects, and as team member in other 20 research projects; > 1700 citations. , h-index 24 (ISI Web of Science). Personal link: https://www.brainmap.ro/ioan-stamatin

The project goal is to develop novel nanostructured oxide layers and porous surfaces with tunable morphology and chemical state on polycrystalline Cu using oxygen and hydrogen plasmas. The project aims at providing a better understanding of active sites, elucidation of reaction mechanisms during the photo-electrochemical reduction of CO2.

Indicators:

– min 2 scientific papers published in ISI indexed journals,

– 2 conference / poster papers

– 1 patent application based on the knowledge gained during the implementation of the project

Phase I Design and construction of the test bench. Synthesis of nanostructured materials. (Deadline 31.12.2021)

During Phase I / 2021, several Cu based structures were tested and characterized using a new photoelectrochemical cell configuration. The obtained materials were characterized from a morpho-structural and physico-chemical point of view using the following methods: atomic force microscopy (AFM), scanning electron microscopy (SEM), UV-Viz and Raman spectrophotometry, electrochemical measurements (cyclic voltammetry, spectroscopy electrochemical impedance). The results obtained demonstrate the potential of these catalysts based on Cu nanostructures for the electrochemical reduction of CO2. In the next stage, studies will be continued to obtain various Cu-based nanostructures through plasma activation processes and optimize the CO2 conversion process.

Phase II. Study of the fotoelectrochemical CO2 reduction reaction- I (Deadline 31.12.2022)

The synthesis process of the photo-electrocatalyst by anodization was optimized, resulting in a consistent protocol for obtaining the catalyst. A CNC system has also been developed for treating the photocatalyst in an open atmosphere plasma jet. The resulting samples were investigated morphologically by atomic force microscopy. Then, the photo-electrochemical processes of CO2 reduction by copper-based catalysts were studied, by specific electrochemical methods (chronoamperometry and cyclic voltammetry). The products in the photo-electrocatalysis process were analyzed through FT-IR spectrometry and the presence of the sodium formate compound was highlighted as a result of the reaction between the formic acid (produced in the CO2 reduction process) and the carbonate of sodium (from the electrolyte solution). The catalyst layers were morphologically analyzed before and after performing the photoelectrocatalysis tests, to determine the average roughness.

Phase III. Study of the fotoelectrochemical CO2 reduction reaction- II (Deadline 31.05.2023)

The protocol for treatment in O2 plasma was optimized, based on which a Cu nanostructured photocatalyst was synthesized. The next step was to characterize it in terms of photo/electrochemical (Chronoamperometry, Cyclic Voltammetry and Mott-Schottky) and morphological (SEM) properties. By means of qualitative and quantitative techniques, FTIR spectroscopy and titration method, the presence and quantity of the reaction product (HCOOH) obtained from the CO2 reduction process was determined. Quantum efficiency (photon to electron conversion efficiency) and Faradaic efficiency were also evaluated. The results obtained in this step have been disseminated as follows: 3 oral presentations at national conferences and 1 patent application registered at OSIM.