The Surendranath Group 🥭

@jacs.acspublications.org

Concerted Proton–Electron Transfer Minimizes Substituent Effects on Adsorbed Phthalocyanine Electrocatalysis Molecularly modified electrodes (MMEs) are potent electrocatalysts, but few principles exist for their rational design. Electrocatalysis by soluble molecules depends strongly on substituents that tune the catalyst redox potential (E1/2), but it is unclear if this parameter similarly impacts MME catalysis. Herein, we employ the hydrogen evolution reaction (HER) as a test case for comparing carbon-adsorbed cobalt phthalocyanine (CoPc/C) and cobalt hexadecafluoro-phthalocyanine (CoFPc/C). By correlating HER activity and voltammetric data to total Co surface concentration across a wide range of catalyst loadings, we find that only 5–25% of adsorbed Co sites contribute to the Co(II/I) redox wave and that this subpopulation poorly correlates with catalytic activity. Instead, in the low-loading limit, catalytic activity correlates linearly with the majority Co(II/I)-silent Co population, revealing per-site turnover frequency (TOF) values for HER. Despite a 230 mV difference in Co(II/I) redox potentials, CoPc/C and CoFPc/C display TOF values differing by less than a factor of 3 when compared over a wide potential range. Mechanistic studies point to an inner-sphere concerted proton–electron transfer step as rate-determining, suggesting that the Co–H bond dissociation free energy (BDFE) rather than the Co(II/I) E1/2 is thermodynamically relevant. Computational studies indicate that the fluoro-substituents lead to compensatory changes in Co(II/I) E1/2 and Co(I) basicity, leaving the Co–H BDFE largely unchanged between CoPc and CoFPc and thereby manifesting in similar catalytic rates. These results highlight the limited effect of E1/2-tuning on MME catalytic activity and motivate the development of methods to directly alter active site–substrate BDFE.

pubs.acs.org/doi/full/10.... #echemsy #electrochemistry #catalysis #chemistry #mit

Congrats Vennela Mannava and Joel Gardner!

By varying the electron donicity of the peripheral substituents on cobalt phthalocyanine, demonstrated that metal-hydrogen BDFE, rather than catalyst E(1/2), is the primary parameter that governs the HER activity of adsorbed molecular electrocatalysts.

Surendranath Group | LinkedIn Surendranath Group | 318 followers on LinkedIn. An electrochemistry lab @MIT Chemistry | Global challenges in the areas of chemical catalysis, energy storage and utilization, and environmental steward...

Follow our page on LinkedIn! www.linkedin.com/company/sure...

Ion-exchange-mediated pre-association gates interfacial PCET The rate of interfacial proton-coupled electron transfer (I-PCET) to a graphite-conjugated carboxylic acid electrode depends on the concentration of nominally innocent supporting NaClO4 electrolyte. T...

@cellpress.bsky.social www.cell.com/chem/abstrac...

Ion-exchange-mediated pre-association gates interfacial PCET The rate of interfacial proton-coupled electron transfer (I-PCET) to a graphite-conjugated carboxylic acid electrode depends on the concentration of nominally innocent supporting NaClO4 electrolyte. T...

Congrats Noah Lewis and Joel Gardner!

Using GCCs, they show interfacial proton coupled electron trans., often rate limiting in HER & aqueous electrocatalysis, is a multistep reaction wherein mechanistic substeps involving the transit of electrolyte ions into/out of the EDL control overall rates.

A simplified, stylized periodic table of elements where large groups of elements are color-coded. Hydrogen (H) is isolated. Group 1 (alkali metals) is labeled "BOOM!". Group 2 (alkaline earth metals) is "rocks & sand & glass & stuff". The transition metals are split into sections: "the foundations of human civilization," "catalysts & superalloys," "ooh, shiny!," "expensive," and "heavy metal poisoning." Technetium (Tc) is boxed separately. The p-block is also grouped: "chips (not tasty kind)," "organic chemistry," and "useful for poisoning your husband." The noble gases are labeled "n o p e." The heaviest elements in the s-block and p-block are labeled "cancer 2" and "cancer alley," with the exception of Bismuth. The transactinides are labeled "more physics than chemistry." The bottom f-block (lanthanides and actinides) is also labeled. The lanthanides are "except for Pm these are all basically the same element," with Promethium (Pm) boxed. The actinides are labeled "rxtors & bombs" and "you probably work at Los Alamos."

please don't @ me like "actually cerium is unique among the lanthanides for its +4 oxidation state"

⚗️🧪 #chemsky

Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer - Nature Chemistry Heterolytic hydrogenations are a key reaction class that includes CO2 reduction to formate and NADH regeneration, yet the mechanism remains unclear. Now it has been shown that this class of thermochemical reactions proceeds through an electrochemical mechanism, with polarization-driven, interfacial hydride transfer as the rate-determining step.

Check it out on Nature Chemistry www.nature.com/articles/s41...

#echemsky

Thermochemical heterolytic hydrogenation catalysis proceeds through polarization-driven hydride transfer - Nature Chemistry Heterolytic hydrogenations are a key reaction class that includes CO2 reduction to formate and NADH regeneration, yet the mechanism remains unclear. Now it has been shown that this class of thermochemical reactions proceeds through an electrochemical mechanism, with polarization-driven, interfacial hydride transfer as the rate-determining step.

Congrats Hai-Xu Wang!

CO₂ hydrogenation to formate and NAD⁺ hydrogenation to NADH — long considered purely non-electrochemical heterolytic hydrogenations — can actually follow an electrochemical mechanism, coupling oxidative hydrogen oxidation (HOR) and reductive hydrogen reduction reactions (HRR)!

Reversible Interfacial Hydride Transfer as a Complementary Tool To Measure Molecular Hydricity Hydride transfer is an essential elementary reaction across the chemical value chain, but there are limited methods available for quantifying thermodynamic hydricity (ΔGH–), particularly among main gr...

pubs.acs.org/doi/10.1021/... @jacs.acspublications.org

Reversible Interfacial Hydride Transfer as a Complementary Tool To Measure Molecular Hydricity Hydride transfer is an essential elementary reaction across the chemical value chain, but there are limited methods available for quantifying thermodynamic hydricity (ΔGH–), particularly among main gr...

Congratulations to Hye Won Chung and Dr. Hai-Xu Wang!

Using hydrogen reduction reaction (HRR), where H2 interconverts w/ hydrides, they developed a potentiometric method to quantify molecular hydricity, applied it to substrates including formate & borohydrides, and investigated solvent-dependence.

Congrats Kunal!

Congrats Dr. Deiaa Harraz!

paper: Molybdenum and Vanadium Do Not Replace Tungsten in the Catalytically Active Forms of the Three Tungstoenzymes in the Hyperthermophilic Archaeon Pyrococcus furiosus Hmmm...you know what the problem is? M You got it set to 'M' for Molybdenum W when it should be set to.. W for Wungsten

13/ Come on SpongeBob! You know: I wungsten, you wungsten, he/she/me wungsten...

doi.org/10.1128/jb.1...

⚗️🧪 #chemsky

Omnipath H2 aims to revolutionize the midstream hydrogen industry based on a technology developed in the Surendrath group. We congratulate the team for winning 2nd place at this year’s MIT Climate & Energy Prize.

reddit /r/chemistry post: Can isotopes of the same element bind together? For example, can an O2 compound be composed of an oxygen-14 atom and an oxygen-16 atom? Top reply from /u/Tortenn: Yes, but one half weighs more so it will tip over

59/ kemistry ⚗️🧪👍

Yogesh Surendranath @ChemistryMIT @interphases.org opens the Spring Meeting #sm25 of @swisschemistry.bsky.social with ‚Using Electrochemistry to Understand and Control Thermochemical Catalysis‘ @unibe.ch

Electrocatalysis Goes Nuts While searching for new nanoelectrocatalysts with outstanding performance, researchers often disregard the complexity and true usability of such materials. Here, it is argued that the chemical and str...

they did oxygen evolution on a hazelnut

[to prove the point that it's meaningless it is to interpret electrocatalytic data from poorly defined complex electrode materials]

#chemsky ⚗️🧪

pubs.acs.org/doi/10.1021/...

Organic chemists when they see a coloured solution in the lab: :0

112/ #chemsky ⚗️🧪

Surprise discovery could lead to improved catalysts for industrial reactions Upending a long-held supposition, MIT researchers discovered that a common catalyst works by cycling between two different forms. The finding could lead to improved catalysts for industrial reactions.

Check out this MIT News page about our recent paper:

news.mit.edu/2025/surpris...

Great Perspective from Cathy Tway & Sorin Filip here too www.science.org/doi/10.1126/...

#chemsky #echemsky #electrochemistry #chemistry

@science.org

Thank you!

Homogeneous-heterogeneous bifunctionality in Pd-catalyzed vinyl acetate synthesis Presently, mechanistic paradigms in catalysis generally posit that the active species remains either homogeneous or heterogeneous throughout the reaction. In this work, we show that a prominent indust...

Fascinating chemsky paper in @science.org today from @interphases.org meticulously revealing that vinyl acetate synthesis operates through tandem homogeneous and heterogeneous palladium catalysis 🧪

www.science.org/doi/10.1126/...

Homogeneous-heterogeneous bifunctionality in Pd-catalyzed vinyl acetate synthesis Presently, mechanistic paradigms in catalysis generally posit that the active species remains either homogeneous or heterogeneous throughout the reaction. In this work, we show that a prominent indust...

Congratulations our very own Deiaa Harraz, Kunal Lodaya, Bryan Tang for their new paper in Science!

Check out our new paper titled Homogeneous-heterogeneous bifunctionality in Pd-catalyzed vinyl acetate synthesis

www.science.org/doi/10.1126/...

We have a new LinkedIn page! Check it out here www.linkedin.com/company/sure...

molecular C18 ring with alternating C-C single and triple bonds

[1/2] aromaticity question for #chemsky:

consider this annular carbon allotrope C18. let's define p orbitals sigma-bonding tangential to the ring as p_z, those pi-bonding in the plane of the ring to be p_y, and those pi-bonding perpendicular to the plane of the ring to be p_x.