@article {45762, title = {Selective synthesis of WO3 and W18O49 nanostructures: ligand-free pH-dependent morphology-controlled self-assembly of hierarchical architectures from 1D nanostructure and sunlight-driven photocatalytic degradation}, journal = {CrystEngComm}, volume = {19}, year = {2017}, month = {APR }, pages = {2096-2105}, type = {Article}, abstract = {

In this study, simple inorganic routes for the synthesis of WO3 and W18O49 nanostructures with variable size and self-assembly are reported. The morphologies and formation of stoichiometric WO3 as well as substoichiometric W18O49 single-crystal phase could be controlled by changing the pH of the reactions medium. This synthesis strategy has the advantages that it is one step, aqueous medium-based, and requires no surfactant or stabilizing agent. Furthermore, it also enables the self-assembly of 1D nanorods of WO3 and W18O49 into hierarchical nanostructures as nanorods bundles, cocoons, urchins, fishbones, etc. This synthesis method may open up a new way to control and tune the stoichiometric and substoichiometric composition of metal oxide nanostructures. Efficient sunlight-driven photocatalytic performance to degrade Rhodamine B (100 mL; 40 mg L-1.) with these tungsten oxide nanostructures was also demonstrated.

}, issn = {1466-8033}, doi = {10.1039/c6ce02518h}, author = {Shirke, Yogita Manikrao and Mukherjee, Shatabdi Porel} } @article {46089, title = {Size-controlled cobalt ferrite nanocrystals: magnetically separable reusable nanocatalysts for selective oxidation of styrene}, journal = {ChemistrySelect}, volume = {4}, year = {2019}, month = {JUN }, pages = {6524-6531}, type = {Article}, abstract = {

Superparamagnetic cobalt ferrite (CFO) nanocrystals (NCs) with sizes similar to 6 nm and similar to 4 nm were synthesized using a facile solvothermal method using fatty acids, lauric acid and stearic acid, as the capping agents. The synthesized nanocrystals were well characterized by XRD, FT-IR, XPS, SEM and TEM. The formation mechanism was explored and it was shown that the fatty acid was actually chemisorbed as a carboxylate onto the surface of CFO NCs. The experimental results specify that the size and size distribution of the CFO NCs were highly dependent on the length of fatty acid hydrophobic chain. Corresponding changes of the magnetic properties were investigated by measuring magnetization as a function of field and temperature, which suggest that the CFO NCs were superparamagnetic in nature. The catalytic properties for the oxidation of styrene in organic medium were examined by using the synthesized CFO NCs with sizes similar to 6 nm and similar to 4 nm. The synthesized CFO NCs, well dispersible in organic media, were demonstrated to be highly catalytically active, reached 100\% conversion of styrene in 12 h with similar to 77\% and similar to 82\% selectivity for styrene oxide respectively. The magnetic CFO nanocatalysts were easily separated and recovered from the reaction medium by an external magnet, and reused for several cycles without losing catalytic selectivity for styrene oxide.

}, keywords = {Cobalt ferrite, epoxidation, Fatty acids, magnetic properties, nanocrystals}, issn = {2365-6549}, doi = {10.1002/slct.201900714}, author = {Jeyavani, Vijayakrishnan and Pawar, Sayali and Dadwal, Arun and Joy, Pattayil Alias and Mukherjee, Shatabdi Porel} } @article {46706, title = {Phase- and morphology-controlled synthesis of tunable plasmonic MoO3-x nanomaterials for ultrasensitive surface-enhanced raman spectroscopy detection}, journal = {Journal of Physical Chemistry C}, volume = {124}, year = {2020}, month = {SEP }, pages = {21082-21093}, type = {Article}, abstract = {

The enhancement of the surface-enhanced Raman scattering (SERS) property of the plasmonic metal oxide semiconductor nanostructures by controlling their phase, shape, size, and oxygen vacancy to detect trace amounts of organics is of significant interest. In this study, a simple surfactant-free hydrothermal strategy was proposed to fabricate crystalline h-MoO3-x and alpha-MoO3-x nanomaterials with tunable plasmonic properties. Herein, the crystal phase, morphology, and oxygen vacancy of MoO3-x nanostructures were precisely controlled under suitable synthetic conditions. The plasmonic properties of the as-synthesized h-MoO3-x and alpha-MoO3-x micro-/nanostructures were controlled by adjusting the residual volume in the autoclaving chamber. In addition, the plasmonic MoO3-x exhibited SERS activity with a detection limit as low as 1.0 x 10(-9) M and the maximum enhancement factor (EF) up to 6.99 x 10(5) for h-MoO3-x, while for alpha-MoO3-x, the detection limit was 1.0 x 10(-7) M with the corresponding EF up to 8.51 x 10(3), comparable with plasmonic noble metal nanomaterials without a {\textquoteleft}{\textquoteleft}hot spot{\textquoteright}{\textquoteright}.

}, issn = {1932-7447}, doi = {10.1021/acs.jpcc.0c06004}, author = {Patil, Manoj Krishnat and Gaikwad, Supriya Hanmant and Mukherjee, Shatabdi Porel} } @article {47786, title = {2D MoO2/N-Doped-carbon nanosheets as SERS tweezers: a non-noble metal reusable substrate for selective organic dye detection}, journal = {ACS Applied Nano Materials}, volume = {4}, year = {2021}, month = {NOV}, pages = {11611 - 11624}, type = {Article}, abstract = {The design and synthesis of a highly sensitive and exceptionally selective surface-enhanced Raman scattering (SERS) substrate with an excellent reusable property are of significant interest because of its vast prospective application in actual and complicated detection environments. Here, a simple synthesis strategy was presented to fabricate crystalline two-dimensional (2D) MoO2/N-doped-carbon nanosheets with the plasmonic property. The morphology, crystal phase, and surface property of MoO2 nanomaterials (NMs) were specifically controlled under suitable reaction conditions. In addition, the plasmonic MoO2/N-doped-carbon NM exhibited a SERS maximum enhancement factor up to 1.38 {\texttimes} 104 with a detection limit as low as 1.0 {\texttimes} 10{\textendash}6 M. More importantly, the as-synthesized nanocomposite shows high selectivity as a {\textquotedblleft}SERS Tweezer{\textquotedblright} toward methylene blue (MB) in binary and ternary mixed interfering analyte solutions, preserving detection sensitivity toward MB for three cycles via an {\textquotedblleft}elect-and-eliminate{\textquotedblright} approach. This strategy will be helpful to design other plasmonic semiconductor NMs for successful tangible applications of selective SERS sensing for trace impurity detections in real and complex environments.}, doi = {10.1021/acsanm.1c02151}, url = {https://doi.org/10.1021/acsanm.1c02151}, author = {Gaikwad, Supriya Hanmant and Mukherjee, Shatabdi Porel} } @article {47035, title = {CsPbBr3/Cs4PbBr6 perovskite@COF nanocomposites for visible-light-driven photocatalytic applications in water}, journal = {Journal of Materials Chemistry A}, volume = {9}, year = {2021}, month = {MAR}, pages = {6819-6826}, type = {Article}, abstract = {

For the first time, we have synthesized all-inorganic CsPbBr3/Cs4PbBr6 perovskite@COF nanocomposites under atmospheric conditions and tuned the crystal structures of the perovskite as well. The nanocomposite is reasonably stable and maintains its crystalline properties even when dipped into water for 60 minutes. The perovskite@COF nanocomposite shows efficient visible-light-driven photocatalytic performance to degrade Methyl orange (10 mL; 20-100 ppm). The rate of photodegradation was about 0.245 min(-1) with high catalytic activity and recyclability for three to six cycles.

}, issn = {2050-7488}, doi = {10.1039/d1ta00201e}, author = {Kour, Prachi and Mukherjee, Shatabdi Porel} } @article {47742, title = {Organic-inorganic perovskitoid with zwitterion cysteamine linker and its crystal-crystal transformation to ruddlesden-popper phase}, journal = {Angewandte Chemie-International Edition}, volume = {60}, year = {2021}, month = {AUG }, pages = {18750-18760}, type = {Article}, abstract = {We demonstrate synthesis of a new low-D hybrid perovskitoid (a perovskite-like hybrid halide structure, yellow crystals, P21/n space group) using zwitterion cysteamine (2-aminoethanethiol) linker, and its remarkable molecular diffusion-controlled crystal-to-crystal transformation to Ruddlesden-Popper phase (Red crystals, Pnma space group). Our stable intermediate perovskitoid distinctly differs from all previous reports by way of a unique staggered arrangement of holes in the puckered 2D configuration with a face-sharing connection between the corrugated-1D double chains. The PL intensity for the yellow phase is 5 orders higher as compared to the red phase and the corresponding average lifetime is also fairly long (143 ns). First principles DFT calculations conform very well with the experimental band gap data. We demonstrate applicability of the new perovskitoid yellow phase as an excellent active layer in a self-powered photodetector and for selective detection of Ni2+ via On-Off-On photoluminescence (PL) based on its composite with few-layer black phosphorous.}, keywords = {Crystal growth, organic-inorganic hybrid composites, perovskite phases, photodetectors, zwitterions}, issn = {1433-7851}, doi = {10.1002/anie.202105918}, author = {Kour, Prachi and Reddy, Mallu Chenna and Pal, Shiv and Sidhik, Siraj and Das, Tisita and Pandey, Padmini and Mukherjee, Shatabdi Porel and Chakraborty, Sudip and Mohite, Aditya D. and Ogale, Satishchandra} } @article {47990, title = {MgB2/NaNO2-PVA free-standing polymer composite film as a green firework: a step towards environmental sustainability}, journal = {Bulletin of Materials Science}, volume = {45}, year = {2022}, month = {SEP }, pages = {175}, type = {Article}, abstract = {

We have demonstrated a simple fabrication methodology of free-standing polymer composite film firework that sparkles, provides colour display and moderate sound, yet is less polluting. The polymer composite film fireworks are composed of magnesium boride (MgB2), sodium nitrite (NaNO2) and poly(vinyl alcohol) (PVA). This study also suggested that a flammable, explosive powder composition can be made of two very common inorganic precursors, mainly NaNO2 and MgB2 . This is the first report demonstrating composite film fireworks with new flammable composition using metal boride as a primary precursor, which can also be used in conventional fireworks fabrication, replacing the traditional fuel, mainly gunpowder. The film fireworks were free from charcoal, sulphur, metal powder and paper. Therefore, they substantially lower the odour and COx, NOx, emissions and minimize the substantial trash generated when burned. Most importantly, film firework{\textquoteright}s minimum ignition temperature and exothermic decomposition temperature are much higher than the ambient temperature; hence are safe to handle.

}, keywords = {Firework, free-standing film, magnesium boride (MgB2), poly(vinyl alcohol) (PVA), sodium nitrite (NaNO2)}, issn = {0250-4707}, doi = {10.1007/s12034-022-02756-8}, author = {Jeyavani, Vijayakrishnan and Kumar, Rajendra and Joy, Pattayil Alias and Mukherjee, Shatabdi Porel} } @article {48344, title = {Scalable mechanochemical synthesis of beta-ketoenamine-linked covalent organic frameworks for methane storage}, journal = {Chemistry-An Asian Journal}, volume = {17}, year = {2022}, month = {DEC}, type = {Article}, abstract = {

In the current scenario of increased pollution and releasing toxic gases by burning petroleum products, switching to natural gas is more promising for reducing CO2 emissions and air pollutants. Hence, research on Liquefied Natural Gas and Compressed Natural Gas is gaining more value. However, natural gas primarily consists of CH4, which has less energy density than conventional fuels. Interestingly, since the C-H ratio of CH4 gas is 1 : 4, it is easily combustible, gives less carbon footprint, and reduces unburnt hydrocarbon pollution. Hence, research on storing and transporting CH4 has utmost importance, and porous materials are one of the suitable candidates for storing CH4. Herein we report the scalable synthesis of highly porous and crystalline covalent organic frameworks for storing CH4 at room temperature and pressure. Two COFs, namely, Tp-Azo and Tp-Azo-BD(Me)(2), synthesized in 1 kg at similar to 45 g batch scale using a Planetary mixer, displayed a maximum BET surface area of around 3345 m(2)/g, and 2342 m(2)/g and CH4 storage of 174.10 cc/cc and 151 cc/cc, respectively. A comparison of the CH4 sorption of Tp-Azo and Tp-Azo-BD(Me)(2) COFs synthesized in different batches has a variation of only +/- 5 cc/cc and shows the consistency in bulk scale synthesis of COFs. The cyclic equilibrium CH4 adsorption studies showed the COFs are stable with consistent CH4 adsorption and desorption cycles. The present study is a step towards the scalable mechanochemical synthesis of COFs for gas storage applications.

}, keywords = {CH4 storage, COF, porous material, scalable synthesis}, issn = {1861-4728}, doi = {10.1002/asia.202201012}, author = {Asokan, Kiran and Patil, Manoj Krishnat and Mukherjee, Shatabdi Porel and Sukumaran, Santhosh Babu and Nandakumar, T.} } @article {48959, title = {Ligand-free one-pot synthesis of Ru/W18O49 self-assembled hierarchical coral-like nanostructures for selective conversion of glucose into glycols}, journal = {ACS Applied Nano Materials }, volume = {6}, year = {2023}, month = {DEC }, pages = {22635-22642}, type = {Journal Article}, abstract = {

In this study, we report a simple inorganic route for the synthesis of Ru/W18O49 self-assembled coral-like nanostructures, with the following advantages: It is one step and requires no surfactant or stabilizing agent; Ru loading is easily tuned, and the as-synthesized nanomaterials can be used as a catalyst without any further processing. The preliminary investigations of the catalytic performance of these as-synthesized Ru/W18O49 nanomaterials appear quite promising for converting glucose to glycols. The total glycol selectivity of 82.6\% with 100\% conversion of glucose was obtained over 0.03 wt \% Ru loading on tungsten nanostructures, which turns out to be the lowest Ru loading\% on support reported to date to achieve the highest total glycol selectivity among the previously reported catalyst based on Ru-nano/composite materials. Additionally, preliminary results show that the concentration of Ru on W18O49 significantly affects the selectivity of the glycol production. Thus, our methodology will open up a wide range of opportunities regarding the choice of metals, stoichiometric/nonstoichiometric WOx (x=1-3) as support, and the viability of further catalytic manipulations. A probable catalytic mechanism for this catalytic process is also proposed.

}, keywords = {glycols, Nanostructure, One-pot synthesis, ruthenium (Ru), selective conversion of glucose, tungsten oxide (W18O49)}, doi = {10.1021/acsanm.3c04200}, author = {Patil, Manoj Krishnat and Gaikwad, Supriya Hanmant and Kirali, Arun Arunima Balachandran and Marimuthu, Banu and Mukherjee, Shatabdi Porel} } @article {49405, title = {Lead-free low-dimensional tetraalkylammonium manganese- and copper-based hybrid organic{\textendash}inorganic perovskites for visual fluorometric Pb2+ ion detection}, journal = {ACS Applied Optical Materials}, volume = {2}, year = {2024}, month = {JUL}, pages = {1533{\textendash}1545}, type = {Article}, abstract = {

For the first time, we have synthesized lead (Pb)-free manganese (Mn)- and copper (Cu)-based hybrid organic{\textendash}inorganic perovskite (HOIP) compounds, compound\ 1, (TEA)2MnBr4, compound\ 2, (TBA)2MnBr4, compound\ 3, (TEA)2CuBr4, and compound\ 4, (TBA)CuBr2\ (where TEA is tetraethylammonium and TBA is tetrabutylammonium), under ambient conditions via mechanochemical synthesis methodology using a Kakuhunter-made planetary mixer. The compounds are characterized as 2D except for (TBA)CuBr2, which has crystallized in the 0D lattice. The synthesized compounds are phase pure and show a stable solid-state emission at room temperature. The Mn-based perovskite compound\ 1\ showed excellent environmental photostability for over a month and reasonable stability under a relative humidity of 70{\textendash}80\%. The nanoparticle (NP) dispersions of compounds\ 1\ and\ 2\ were used further for fluorescence titration studies using various heavy metal cations, including transition metals and lanthanides (e.g., Y3+, Nb3+, Co2+, Ni2+, Ag+, Zn2+, Cd2+, Pb2+, Gd3+, and Dy3+), where they showed good fluorescence switching by the Pb2+\ ion. Compound\ 1\ demonstrated excellent fluorescence switching performance with Pb2+\ titration with a Pb2+\ detection limit of 2.43 {\texttimes} 10{\textendash}8\ M and hence can be used to fabricate a Pb2+\ calorimetric sensor. A preliminary visual thin film-based sensor using NPs of compound\ 1\ was fabricated to test the change in emission from blue to green in correlation with the results obtained in the NP solution during Pb2+\ ion sensing. A fascinating in situ ion-exchange-based mechanism for the sensitivity of NPs of compound\ 1\ is confirmed. This study reveals the ability of Pb-free Mn-based HOIPs to detect an oxidizing metal cation, Pb2+, efficiently and quantitatively.

}, doi = {10.1021/acsaom.4c00182}, url = {https://pubs.acs.org/doi/10.1021/acsaom.4c00182}, author = {Kour, Prachi and Sahu, Pragati and Dambhare, Neha V. and Rath, Arup Kumar and Mukherjee, Shatabdi Porel} } @article {49025, title = {Remarkable SO2 and H2S resistant ability on CO oxidation by unique Pd/WO3 3D hollow sphere nanocatalyst: correlating structure-activity relationships on SO2 exposure}, journal = {ACS Applied Energy Materials}, volume = {7}, year = {2024}, month = {JAN }, pages = {1476-1487}, type = {Article}, abstract = {

We report a simple inorganic route for synthesizing a Pd/WO3 3D hollow sphere nanocatalyst, where Pd nanoparticles are encapsulated and well distributed on porous tungsten oxide nanospheres. The synthesis protocol has advantages, as it requires no surfactant or stabilizing agent, Pd loading is easily tuned, and the as-synthesized nanomaterials can be directly used as catalysts for the CO oxidation reaction. The synthesized nanocatalyst exhibited 100\% CO to CO2 conversion efficiency at 260 degrees C. In addition, the nanocatalyst demonstrated remarkable SO2 (3 ppm) tolerance during the CO oxidation reaction for prolonged SO2 sulfation of 1-21 h at 260-400 degrees C. This represents the longest SO2 exposure time reported to date based on a single metal Pd/support-based nanocatalyst. No decrement in CO conversion efficiency was observed even after SO2 (3 ppm) treatment for 21 h for the first time based on a single metal Pd-based nanocatalyst. Moreover, the synthesized nanocatalyst shows H2S (4 ppm), even in situ H2S tolerance during the CO oxidation reaction at 260 degrees C for 1-3 h and exhibited less sensitivity to prolonged and stringent sulfur exposure, with the highest H2S concentration and maximum 100\% CO to CO2 conversion efficiency obtained after H2S treatment for the first time based on a Pd-based nanocatalyst to the best of our knowledge. The composition and structure of the R-Pd/WO3 nanocatalyst were not much influenced, even after the prolonged SO2 and H2S exposure during the CO oxidation reaction, as verified from spent catalyst analysis. Finally, our DFT-based model provides insights into understanding the observed sulfur resistance on Pd/WO3 by analyzing the underlying electronic structure. Therefore, our strategic synthesis methodology will open up many opportunities to select Pd/metal oxide-based nanomaterials for designing highly efficient, stable, and SO2/H2S-resistant nanocomposite catalyst.

}, keywords = {CO oxidation, DFT calculation, nanocatalyst, palladium (Pd), SO2 andH(2)S resistant ability, structure-activityrelationships, tungstenoxide (WO3)}, issn = {2574-0962}, doi = {10.1021/acsaem.3c02664}, author = {Jeyavani, Vijayakrishnan and Kondhekar, Deepali and Bhati, Meema and Dev, Sahil and Joshi, Kavita and Devi, R. Nandini and Mukherjee, Shatabdi Porel} }