Advancements in Electrocatalysis Technology

Earlier this week, in collaboration with Prof. Hongliang Xin (Virginia Tech Department of Chemical Engineering) and Dr. Luxi Li (Advanced Photon Source), we published a research article in Nature Catalysis to report a new discovery at the electrochemical solid–liquid interface: https://lnkd.in/euiCCgfm. After years of work across three generations of graduate students and postdocs, the paper is finally online! 🐶 Electrode materials are more dynamic than we thought, especially at the solid–liquid interface. We can use such dynamics. For decades, we have focused on optimizing bulk composition and surface structure in battery and electrocatalysis research. But what if the real key to performance lies in something far less visible and far more dynamic? In NiFe-based electrodes used for the oxygen evolution reaction (OER), a long-standing mystery has been the role of mobile Fe species that leach into the electrolyte. Until now, these dissolved species at the solid–liquid interface have been notoriously difficult to pin down. Characterizing them, let alone proving their function, has been a major experimental challenge. This Nature Catalysis study finally does it. It reveals a solid–molecular mechanism for OER: Fe species dynamically dissolve, interact in the liquid phase, and re-engage in the reaction, helping drive water oxidation in a cooperative manner with the solid surface. This fundamentally shifts how we approach electrode design, essentially not as static solids but as evolving systems with active, mobile participants in the electrolyte. For researchers, this opens new frontiers:    How do we observe and quantify species at the interface in real time?    Can we design materials to intentionally release beneficial mobile species?    Could this concept apply more broadly, beyond OER and beyond Fe? If we want to push performance boundaries, we need to better understand not just what is on the surface, but what is happening beyond it. #Electrochemistry #MaterialsScience #BatteryResearch #Electrocatalysis #OER #EnergyMaterials #InterfaceScience #InSituCharacterization #SolidMolecularMechanism #BeyondTheSurface

Metal–organic frameworks (MOFs) are promising candidates for electrocatalysis due to their high surface area, tunable pore structures, and chemical modularity, which enable selective adsorption and activation of reactant molecules such as CO₂. Their structural versatility also allows for the incorporation of catalytic metal centers, including single-atom sites, potentially enhancing reaction pathways. However, the widespread application of MOFs in electrochemical CO₂ reduction has been hampered by their inherently low electrical conductivity and structural instability under reductive conditions, particularly in aqueous systems where competitive hydrogen evolution further limits product selectivity. Our recent publication (https://lnkd.in/gCgNJh3Q) overcomes these limitations by employing a Cu-metalated porphyrinic Zr-MOF (PCN-222(Cu)) in a non-aqueous electrochemical system, where enhanced CO₂ solubility and suppressed hydrogen evolution allow for greater control of proton-coupled electron transfer processes. The integration of Cu single-atom sites within the conductive Zr-porphyrin framework enables the formation of multivariate C₂ products—acetate, glyoxylate, glycolate, and oxalate—with Faradaic efficiency (up to 40% for acetate) and high current densities (~100 mA cm⁻²). Spectroscopic and mechanistic analyses confirm that the synergy between the Cu active sites and the Zr node-driven proton environment facilitates deep CO₂ reduction via stabilized intermediates and controlled proton delivery. Congratulations to the team – Rajan R. Bhawnani, Rohan Sartape, Vamsi Vikram Gande, Michael L. Barsoum, Elias Kallon, Roberto dos Reis, and Vinayak Dravid for setting a new benchmark for MOF-based CO₂ electroreduction in non-aqueous media and providing a molecular-level design strategy for next-generation catalysts capable of producing multi-carbon products with industrially relevant activity and selectivity. #CO2Reduction #Electrocatalysis #MOFs #SingleAtomCatalysts #SustainableChemistry

Interfacial Engineering of Pillared Co(II) Metal–Organic Framework@NiMn-Layered Double Hydroxide Nanocomposite for Oxygen Evolution Reaction Electrocatalysis             Inorg. Chem., 64, 361–370 (2025). Clean energy conversion and storage require simple, economical, and effective electrode materials to achieve promising results. The development of high-performance electrocatalysts with adequate stability and cost-effectiveness is essential to ensure low overpotentials toward the oxygen evolution reaction (OER). Herein, a cobalt-based metal–organic framework with 4,4,4-6T14 topology in combination with various ratios of NiMn-layered double hydroxide (Co-MOF@X%NiMn-LDH, X = 5, 10, 20, and 40%) is applied as an effective electrocatalyst for the oxidation of water. The optimum sample, Co-MOF@20%NiMn-LDH nanocomposite, showed an overpotential of 174 mV at a current density of 10 mA cm–2 and a reduced Tafel slope of 64 mV dec–1 in 1 M KOH, which makes it an excellent candidate, significantly superior to commercial IrO2 and most MOF- and LDH-based electrocatalysts. Chronopotentiometry tests for the OER over several hours confirmed that these electrocatalysts have been sufficiently stable. Pillared MOFs can obstruct active entities from NiMn-LDH cubic agglomeration, thus facilitating mass transportation and ensuring the continuous exposure of active sites. Accordingly, the synthesized Co-MOF@20%NiMn-LDH composite demonstrates considerable electrocatalytic efficiency and stability toward the OER, as a consequence of the porous structure, external surface area, and synergistic effects among Co-MOF and NiMn-LDH samples. Read the article here: https://lnkd.in/dpCDxVAb

Synthesis of a 2D #tungsten #MXene, W2TiC2Tx, for electrocatalysis: in this updated preprint (https://lnkd.in/gcCsZ7NV), with our additional experiments, calculations, and characterizations, we show this new MXene is the first out-of-plane ordered double metal MXene with W in the outer M3C2 layers. It also outperforms all other MXenes in hydrogen evolution reaction (HER) performance. We now know precisely what is being etched out from its non-MAX covalently bonded precursor (W,Ti)4C4-y, how the precursor is formed, and how to eliminate the oxygen presence in the precursor and promote more W vacancies, which are key for successful MXene synthesis. Read more in the main text and the SI: https://lnkd.in/gcCsZ7NV This is another major collaborative effort between my excellent postdocs and students and our wonderful collaborators. Dr. Anupma Thakur, Wyatt Highland, Brian C. Wyatt, Jiayi Xu, Nithin Chandran B S, Zachary Hood, Shiba P Adhikari, Emad Oveisi, Ph.D., Barbara Pacáková, Jeffrey Simon, Colton Fruhling, Mohammad Asadi, Ph.D., Paweł Piotr Michałowski, Vladimir Shalaev, Alexandra Boltasseva, Thomas Beechem, Cong Liu Thank you to Mostafa Dadashi Firouzjaei for designing the graphical abstratc. Purdue University School of Materials Engineering Purdue University Mechanical Engineering Purdue University Elmore Family School of Electrical and Computer Engineering Argonne National Laboratory

Our latest article has been published in Energy & Environmental Science! In this work, Ziqing Lin reports experimental methods to determine the reaction energetics of oxygen-evolving electrocatalysts. Our approach focused on developing electroadsorption analysis models to fully describe the complex redox profile of oxygen-evolving electrocatalysis, which were used to understand the reactivity of ruthenium oxides incorporating first-row transition metals. These experiments enabled the determination of binding energies for *OH, *O, and *OOH intermediates, as well as their corresponding energy scaling relations. We used this information to design an FeMn-RuOx electrocatalyst with an 876% increase in mass activity compared to RuO2. We expect that electroadsorption analysis will become a useful tool to guide the design of next generation electrocatalysts and help bridge the gap between experimental energetics and theoretical predictions. Many thanks to Vitaly Alexandrov and Payal Chaudhary for theoretical studies on Fe-Mn-Ru oxide surfaces! Link below: https://lnkd.in/eMihcbue

Thrilled to announce another recent publication: Iridium Oxide Coordinatively Unsaturated Active Sites Govern the Electrocatalytic Oxidation of Water In this study, we utilized a specialized membrane electrode assembly to conduct operando X-ray absorption and resonant photoemission spectroscopy on mesoporous iridium oxide films, calcined at various temperatures. By combining these measurements with ab initio simulations, we could distinguish between µ2-O (bridging oxygen) and µ1-O (terminal oxygen) in the catalysts' near-surface regions. Our findings reveal that the intrinsic activity of iridium oxide correlates with the formation of µ1-O species, active in O−O bond formation during the oxygen evolution reaction (OER). Notably, we observed that peroxo species do not accumulate under reaction conditions, emphasizing the importance of µ1-O species in the electrochemical oxidation of water. This research underscores the need to integrate theoretical approaches with operando measurements to gain a comprehensive understanding of catalyst surfaces during operation. A big thank you to all the authors and collaborators for their hard work and dedication! Read more about our findings here: (https://lnkd.in/eSgydmN3) #Electrocatalysis #Nanotechnology #AdvancedEnergyMaterials