02539nas a2200289   4500008004100000022001400041245014400055210006900199260000900268300001600277490000700293520157100300653002101871653001301892653001901905653001301924653001401937653000801951100002301959700002101982700001802003700002302021700001902044700002802063700003002091856012802121       2024                        eng d  a1944-824400aElectrocatalytic glycerol conversion: a low-voltage pathway to efficient carbon-negative green hydrogen and value-added chemical production0 aElectrocatalytic glycerol conversion a lowvoltage pathway to eff  cMAY   a26130-261410 v163 a<p>
	Electrochemical glycerol oxidation reaction (GLYOR) could be a promising way to use the abundantly available glycerol for production of value-added chemicals and fuels. Completely avoiding the oxygen evolution reaction (OER) with GLYOR is an evolving strategy to reduce the overall cell potential and generate value-added chemicals and fuels on both the anode and cathode. We demonstrate the morphology-controlled palladium nanocrystals, afforded by colloidal chemistry, and their established morphology-dependent GLYOR performance. Although it is known that controlling the morphology of an electrocatalyst can modulate the activity and selectivity of the products, still it is a relatively underexplored area for many reactions, including GLYOR. Among nanocube (Pd-NC), truncated octahedron (Pd-TO), spherical and polycrystalline (Pd-PC) morphologies, the Pd-NC electrocatalyst deposited on a Ni foam exhibits the highest glycerol conversion (85%) along with 42% glyceric acid selectivity at a low applied potential of 0.6 V (vs reversible hydrogen electrode (RHE)) in 0.1 M glycerol and 1 M KOH at ambient temperature. Owing to the much favorable thermodynamics of GLYOR on the Pd-NC surface, the assembled electrolyzer requires an electricity input of only similar to 3.7 kWh/m(3) of H-2 at a current density of 100 mA/cm(2), in contrast to the requirement of &gt;= 5 kWh/m(3) of H-2 with an alkaline/PEM electrolyzer. Sustainability has been successfully demonstrated at 10 and 50 mA/cm(2) and up to 120 h with GLYOR in water and simulated seawater.</p>
10aelectrocatalysis10aGlycerol10agreen hydrogen10ananocube10aPalladium10aSDG1 aChauhan, Inderjeet1 aBajpai, Himanshu1 aRay, Bishakha1 aKolekar, Sadhu, K.1 aDatar, Suwarna1 aPatra, Kshirodra, Kumar1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/electrocatalytic-glycerol-conversion-low-voltage-pathway-efficient-carbon-negative-green02989nas a2200277   4500008004100000022001400041245016400055210006900219260000800288300001100296490000800307520198800315653002502303653002102328653002202349653001902371100002302390700002802413700002902441700002102470700001802491700001802509700002602527700003002553856012802583       2026                        eng d  a1385-894700aPotential tuneable glucose oxidation to selective C6 molecules and CC cleavage, and parallel green H2 production: sustainable high current density electrolysis0 aPotential tuneable glucose oxidation to selective C6 molecules a  cFEB  a1726330 v5293 a<p>
	Current study elucidates the electrocatalytic efficacy of palladium-nanocubes (Pd-NCs) for the selective oxidation of glucose to value-added chemicals with concomitant hydrogen evolution. The Pd-NC catalyst demonstrated exceptional activity and product selectivity, achieving nearly quantitative glucose conversion (&gt;99 %) with high gluconic and glucaric acid yield at low anodic overpotential (0.6 V vs. RHE) in alkaline electrolyte. At not-so-high elevated potentials (1.2 V vs. RHE), oxidative CC scission prevails, yielding shorter-chain carboxylates along with C6-acids. Reaction products are thoroughly characterized and quantitatively estimated by NMR spectral methods; NMR methods also provide CC cleavage and mechanistic pathways of glucose to various products. Complementary DFT calculations delineate the thermodynamic favorability of glucose adsorption on Pd-NC surfaces (-1.83 eV) and the exergonic oxidation pathway under applied bias, corroborating experimental product distributions. In a two-electrode electrolyzer, Pd-NC anode paired with Pt/C and Ni2P cathode demonstrates 100 mA/cm(2) at 0.99 V and 1.37 V, respectively, with 48 % reduction in energy input (26.6 kWh/kg H-2) compared to conventional alkaline electrolysis; critically, H-2 production energy is lower than the usable energy (33.3 kWh/kg H-2). Sustainable chronopotentiometric assays confirm sustainability (similar to 140 h) in alkaline as well as saline electrolytes, underscoring the system's resilience against chloride-mediated corrosion. Present work establishes a proof of concept for integrated biomass-component valorization and carbon-negative green hydrogen production, merging atomic-level mechanistic insights with scalable reactor design. Optimization of reaction parameters, including potential tuning, reaction temperature and electrolyte engineering, offers a compelling strategy to further enhance C6 and fragmented product selectivity and overall system efficiency.</p>
10abiomass valorization10aelectrocatalysis10aenergy conversion10aSustainability1 aChauhan, Inderjeet1 aPatra, Kshirodra, Kumar1 aVijay, Pothoppurathu, M.1 aNalajala, Naresh1 aMehta, Shweta1 aJoshi, Kavita1 aRavindranathan, Sapna1 aGopinath, Chinnakonda, S.  uhttps://library.ncl.res.in/content/potential-tuneable-glucose-oxidation-selective-c6-molecules-and-cc-cleavage-and-parallel