00638nas a2200157 4500008004100000022001400041245013000055210006900185260000800254300001000262490000600272100001800278700002600296700003100322856012700353 2020 eng d a2168-048500aSolvent-less solid state synthesis of dispersible metal and semiconducting metal sulfide nanocrystals (vol 6, pg 12006, 2018)0 aSolventless solid state synthesis of dispersible metal and semic cNOV a170000 v81 aBera, Abhijit1 aBusupalli, Balanagulu1 aPrasad, Bhagavatula, L. V. uhttps://library.ncl.res.in/content/solvent-less-solid-state-synthesis-dispersible-metal-and-semiconducting-metal-sulfide-001915nas a2200145 4500008004100000245012900041210006900170260000800239300001400247490000700261520140500268100002401673700003101697856004101728 2022 eng d00aSelective electro-oxidation of phenol to 1,4-hydroquinone employing carbonaceous electrodes: surface modification is the key0 aSelective electrooxidation of phenol to 14hydroquinone employing cJAN a2518-25250 v463 aThe oxidation of phenol leading to 1,4-hydroquinone with high conversion, remarkable selectivity and an excellent yield (87% isolated) has been accomplished under electrolytic conditions in an aqueous medium employing carbon-based electrodes. To achieve this, various factors such as electrode stability, repeatability, and the type of product formed by the electrochemical oxidation of phenol have been investigated using cyclic voltammetry first and then organic transformations under optimized conditions were accomplished by constant current electrolysis. The voltammetric data clearly show that electrochemically generated intermediates passivate the surface of the typically used electrodes, leading to a decrease in their activity, which is a major problem concerning the transformation of phenol electro-oxidation to an industrially adaptable process. In this work, it is established that such difficulties could be circumvented using surface modified carbonaceous electrodes having disordered graphene-like structures and oxygen functional groups. It is also demonstrated that surface modified reticulated vitreous carbon (RVC) based electrodes could be used for electro-oxidation of phenol at a reasonably large scale. The electrolysis conditions have been optimized based on the mechanistic understanding leading to remarkable conversion of phenol with 87% selectivity to 1,4-hydroquinone.1 aBaravkar, Mayur, D.1 aPrasad, Bhagavatula, L. V. uhttp://dx.doi.org/10.1039/D1NJ04640C01855nas a2200157 4500008004100000022001400041245010600055210006900161260000800230300001400238490000700252520125400259100002701513700003101540856012601571 2023 eng d a0306-001200aSurface functionalization of inorganic nanoparticles with ligands: a necessary step for their utility0 aSurface functionalization of inorganic nanoparticles with ligand cAPR a2573-25950 v523 a

The importance of organic ligands in protecting inorganic nanoparticles and thus imparting the needed stabilization as colloidal dispersions was realised many years ago. Currently, the rational preparation of such nanoparticles with designed organic molecules/ligands resulting in the formation of functional nanoparticles (FNPs) that are tuned for a specific application is an area of immense research interest. The preparation of such FNPs for a desired application requires a clear understanding of the interactions at the nanoparticle (NP)-ligand and ligand-solvent interfaces, and demands a deep appreciation of the surface science and coordination chemistry. In this tutorial review, we briefly explore the evolution of surface-ligand chemistry and inform the readers that, apart from protecting the surface, ligands can modulate the physico-chemical properties of the underlying inorganic NPs as well. This review further presents the design principles for the rational preparation of such FNPs, where one or more ligand shells can be added to the nanoparticle surface, thereby improving the adaptability and amenability of the NP exterior towards the environment in which they are present, as required for a specific application.

1 aBhattacharjee, Kaustav1 aPrasad, Bhagavatula, L. V. uhttps://library.ncl.res.in/content/surface-functionalization-inorganic-nanoparticles-ligands-necessary-step-their-utility02800nas a2200277 4500008004100000245017100041210006900212260000800281300001600289490000600305520175600311653002502067653002802092653003102120653003102151653002402182653002802206653002002234100001702254700001802271700002002289700002702309700003102336700002602367856012902393 2025 eng d00aStrategic design of a single-source precursor for in situ generation and integration of adherent species on Ni3S4 entangled-nanosheets for energy storage applications0 aStrategic design of a singlesource precursor for in situ generat cOCT a19943-199510 v83 a

Synthesizing transition-metal chalcogenides (TMC) via a single-source precursor (SSP) route has shown great potential due to better reproducibility and control over stoichiometry, phase, and morphology. While the SSP converts into TMC, surfactants or coordinating species are essential to ensure dispersibility for further solution-based processing protocols. These additional species are typically highly toxic, difficult to remove, and adversely affect device performance. Here, as a proof of concept, design-induced in situ stabilized Ni3S4 (DiSNi) protocol demonstrates that strategic SSP design and optimized reaction conditions can facilitate directed chemical reactivity, gradually generating adhering species, which seamlessly integrate onto the metal chalcogenides, aiding the formation of stable dispersions without utilizing additional stabilizers. The proposed mechanism is validated by detailed strategic experiments and analysis, like X-ray photoelectron spectroscopy (XPS), accelerated dispersion stability measurements, and postsynthesis base treatment, which confirm the presence of in situ generated diethylammonium ion (DEA+) as the adherent and corroborate its role in dispersibility. The obtained Ni3S4 entangled-nanosheets are utilized to fabricate additive-free symmetric supercapacitors with organic electrolyte for charge storage over an extended potential window of 2.8 V and an energy density of 12.44 mu W h cm-2 at a power density of 0.42 mW cm-2. The devised DiSNi protocol showcases the importance of the SSP design for achieving multifunctionality. It is anticipated to have a broader impact on the role of careful design of SSP, making it an ideal contender for synthesizing transition-metal chalcogenides.

10adispersion stability10aenergy storages devices10alow-boiling point solvents10anickel sulfide dispersions10aorganic electrolyte10asingle-source precursor10aSupercapacitors1 aSingh, Rahul1 aThakur, Rohit1 aSahu, Umasharan1 aSahoo, Ramesh, Chandra1 aPrasad, Bhagavatula, L. V.1 aMatte, H., S. S. Rama uhttps://library.ncl.res.in/content/strategic-design-single-source-precursor-situ-generation-and-integration-adherent-species02263nas a2200217 4500008004100000022001400041245014400055210006900199260000800268490000700276520145500283653002101738653000801759653002401767653002701791100002101818700002001839700002401859700003101883856013101914 2025 eng d a1613-681000aSynthesis framework for designing PtPdCoNiMn high-entropy alloy: a stable electrocatalyst for enhanced alkaline hydrogen evolution reaction0 aSynthesis framework for designing PtPdCoNiMn highentropy alloy a cJAN0 v213 a

High entropy alloys (HEAs) are an emerging class of advanced materials characterized by their multifunctionality and potential to replace commercial catalysts in electrocatalytic water splitting. The synergy among the various alloyed elements in HEAs makes them particularly promising for applications in electrocatalysis. However, preparation of HEA via bottom-up approaches by avoiding the formation of mono, di, and tri metallic alloys in the nanoscale is challenging. This aspect is addressed, in this study by exploring the logical selection of solvents, reducing agents, and capping agents, along with their relative fractions, in the solvothermal synthesis of the HEA comprising platinum-palladium-cobalt-nickel-manganese (PtPdCoNiMn). It is established that the reducing capabilities of both the solvent and reducing agent are crucial for the reduction of each metal to form a single-phase HEA. The synthesized HEA (20 wt.%)/functionalized carbon (FC) demonstrates excellent performance as an HER catalyst, exhibiting a low overpotential of 48.7 mV at -10 mA cm-2 in an alkaline electrolyte. This performance is characterized by high reaction kinetics and stability at elevated current densities. Furthermore, the catalyst shows impressive performance in both simulated and actual seawater. This development reduces the reliance on platinum while enhancing the long-term durability and catalytic efficiency of the electrocatalyst.

10aelectrocatalysts10aHER10ahigh entropy alloys10asolvothermal synthesis1 aChandran, Athira1 aSahoo, Sudeshna1 aSingh, Ashutosh, K.1 aPrasad, Bhagavatula, L. V. uhttps://library.ncl.res.in/content/synthesis-framework-designing-ptpdconimn-high-entropy-alloy-stable-electrocatalyst-enhanced02285nas a2200217 4500008004100000245009800041210006900139260000800208300001200216490000600228520156200234653002301796653001101819653001801830653001201848653001701860100001501877700001901892700003101911856012501942 2026 eng d00aSelf-powered photodetection in AgBiS2 nanocrystals synthesized from AgBi-mixed-metal thiolate0 aSelfpowered photodetection in AgBiS2 nanocrystals synthesized fr cJAN a448-4560 v93 a

AgBiS2 has emerged as a promising optoelectronic material owing to its high absorption coefficient, environmentally friendly and abundant components, offering a sustainable alternative to lead- and cadmium-based chalcogenides. Realizing the full potential of AgBiS2 devices, however, requires scalable synthesis routes that include development of suitable precursors and minimize the use of harsh solvents, elevated temperatures, inert environments, etc. Here, we present a facile, solvent-free synthesis of phase pure AgBiS2 nanocrystals (NCs) at room temperature and under ambient conditions, enabled by the AgBi mixed-metal thiolate (AgBi-MMT) precursor complex. The initial choice of metal salts determines the nature of the metal thiolate intermediate complex, which subsequently influences the quality of the resulting AgBiS2 NCs. As a single-source precursor of the metals, AgBi-MMT enables controlled release of Ag+ and Bi3+ ions, yielding phase-pure AgBiS2 NCs. Furthermore, the MMT that is derived from AgI and BiI3 precursors promotes in situ surface passivation of the AgBiS2 NCs by iodide ions by trapping molecular I2 within its matrix. Under illumination, these iodide ions undergo reversible migration, generating a built-in potential and enabling self-powered photodetection in devices prepared from the as-synthesized NCs. This work expands the synthesis methodology of AgBiS2, highlighting the importance of metal thiolates as precursors in nanomaterial syntheses, and influence of iodine species in photo-operational devices.

10abuilt-in potential10aiodine10aion migration10alayered10aquantum dots1 aDas, Mouli1 aSwathi, S., P.1 aPrasad, Bhagavatula, L. V. uhttps://library.ncl.res.in/content/self-powered-photodetection-agbis2-nanocrystals-synthesized-agbi-mixed-metal-thiolate