02359nas a2200277 4500008004100000022001400041245014700055210006900202260000800271300000800279490000600287520143600293653001501729653001601744653003001760653001401790653001301804653001901817653001801836653002101854100002801875700002101903700001501924700001901939856012301958 2019 eng d a2296-264600aElectrocatalysis of oxygen reduction reaction on shape-controlled pt and pd nanoparticles-importance of surface cleanliness and reconstruction0 aElectrocatalysis of oxygen reduction reaction on shapecontrolled cOCT a6480 v73 a

Shape-controlled precious metal nanoparticles have attracted significant research interest in the recent past due to their fundamental and scientific importance. Because of their crystallographic-orientation-dependent properties, these metal nanoparticles have tremendous implications in electrocatalysis. This review aims to discuss the strategies for synthesis of shape-controlled platinum (Pt) and palladium (Pd) nanoparticles and procedures for the surfactant removal, without compromising their surface structural integrity. In particular, the electrocatalysis of oxygen reduction reaction (ORR) on shape-controlled nanoparticles (Pt and Pd) is discussed and the results are analyzed in the context of that reported with single crystal electrodes. Accepted theories on the stability of precious metal nanoparticle surfaces under electrochemical conditions are revisited. Dissolution, reconstruction, and comprehensive views on the factors that contribute to the loss of electrochemically active surface area (ESA) of nanoparticles leading to an inevitable decrease in ORR activity are presented. The contribution of adsorbed electrolyte anions, in-situ generated adsorbates and contaminants toward the ESA reduction are also discussed. Methods for the revival of activity of surfaces contaminated with adsorbed impurities without perturbing the surface structure and its implications to electrocatalysis are reviewed.

10aAdsorption10aDissolution10aoxygen reduction reaction10aPalladium10aplatinum10areconstruction10ashape-control10asurface cleaning1 aDevivaraprasad, Ruttala1 aNalajala, Naresh1 aBera, Bapi1 aNeergat, Manoj uhttps://library.ncl.res.in/content/electrocatalysis-oxygen-reduction-reaction-shape-controlled-pt-and-pd-nanoparticles02821nas a2200253 4500008004100000022001400041245010600055210006900161260000800230300001600238490000700254520197500261653001202236653001902248653003002267653000902297653002002306100001602326700002102342700002202363700002002385700003002405856013202435 2019 eng d a1944-824400aElectronic integration and thin film aspects of Au-Pd/rGO/TiO2 for improved solar hydrogen generation0 aElectronic integration and thin film aspects of AuPdrGOTiO2 for  cSEP a32869-328780 v113 a

In the present work, we have synthesized noble bimetallic nanoparticles (Au-Pd NPs) on a carbon-based support and integrated with titania to obtain Au-Pd/C/TiO2 and Au-Pd/rGO/TiO2 nanocomposites using an ecofriendly hydrothermal method. Here, a 1:1 (w/w) Au-Pd bimetallic composition was dispersed on (a) high-surface-area (3000 m(2) g(-1)) activated carbon (Au-Pd/C), prepared from a locally available plant source (in Assam, India), and (b) reduced graphene oxide (rGO) (Au-Pd/rGO); subsequently, they were integrated with TiO2. The shift observed in Raman spectroscopy demonstrates the electronic integration of the bimetal with titania. The photocatalytic activity of the above materials for the hydrogen evolution reaction was studied under 1 sun conditions using methanol as a sacrificial agent in a powder form. The photocatalysts were also employed to prepare a thin film by the drop-casting method. Au-Pd/rGO/TiO2 exhibits 43 times higher hydrogen (H-2) yield in the thin film form (21.50 mmol h(-1) g(-1)) compared to the powder form (0.50 mmol h(-1) g(-1)). On the other hand, Au-Pd/C/TiO2 shows 13 times higher hydrogen (H-2) yield in the thin film form (6.42 mmol h(-1) g(-1)) compared to the powder form (0.48 mmol h(-1) g(-1)). While powder forms of both catalysts show comparable activity, the Au-Pd/rGO/TiO2 thin film shows 3.4 times higher activity than that of Au-Pd/C/TiO2. This can be ascribed to (a) an effective separation of photogenerated electron-hole pairs at the interface of Au-Pd/rGO/TiO2 and (b) the better field effect due to plasmon resonance of the bimetal in the thin film form. The catalytic influence of the carbon-based support is highly pronounced due to synergistic binding interaction of bimetallic nanoparticles. Further, a large amount of hydrogen evolution in the film form with both catalysts (Au-Pd/C/TiO2 and Au-Pd/rGO/TiO2) reiterates that charge utilization should be better compared to that in powder catalysts.

10abimetal10aPhotocatalysis10asurface plasmon resonance10aTiO210awater splitting1 aTudu, Bijoy1 aNalajala, Naresh1 aReddy, Kasala, P.1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/electronic-integration-and-thin-film-aspects-au-pdrgotio2-improved-solar-hydrogen-generation01513nas a2200157 4500008004100000245012200041210006900163260001300232300001200245520089400257100002501151700002101176700001901197700002001216856011901236 2019 eng d00aFunctionalization of graphene - a critical overview of its improved physical, chemical and electrochemical properties0 aFunctionalization of graphene a critical overview of its improve bSpringer a139-1733 aGraphene, the 2D allotrope of carbon, is reported to be functionalized with a plethora of organic and inorganic species. This functionalization imparts significant improvement in the physical, chemical and electrochemical properties of graphene. The covalent and non-covalent functionalization of graphene with electron-rich organic moieties and heteroatoms is focused on different sections of this chapter. The focus is laid on the improvement in physical, chemical and electrochemical properties of graphene achieved through this functionalization. The enhancement in electrocatalytic activity of non-metal-doped graphene towards the oxygen reduction reaction, methanol oxidation reaction and photocatalysis is covered. Towards the end, the potential uses of functionalized graphene for selected applications like biosensors, fuel cells and dye-sensitized solar cells are also discussed.1 aSingh, Ramesh, Kumar1 aNalajala, Naresh1 aKar, Tathagata1 aSchechter, Alex uhttps://library.ncl.res.in/content/functionalization-graphene-critical-overview-its-improved-physical-chemical-and01947nas a2200181 4500008004100000022001400041245014500055210006900200260000800269300001400277490000600291520123600297100002101533700002801554700002401582700003001606856012901636 2019 eng d a2046-206900aWhy the thin film form of a photocatalyst is better than the particulate form for direct solar-to-hydrogen conversion: a poor man's approach0 aWhy the thin film form of a photocatalyst is better than the par cFEB a6094-61000 v93 a

We demonstrated an easy method to improve the efficiency of photocatalysts by an order of magnitude by maximizing light absorption and charge carrier diffusion. Degussa titania (P25) and Pd/P25 composite photocatalyst thin films coated over regular glass plates were prepared and evaluated for solar hydrogen production in direct sunlight with aqueous methanol. It is worth noting that only UV light present in direct sunlight (similar to 4%) was absorbed by the catalysts. The hydrogen production activities of catalysts were compared for thin film and particulate forms at 1 and 25 mg levels. The hydrogen yield values suggested that 1 mg thin film form of Pd/P25 provided 11-12 times higher activity than 25 mg powder form. Comparable light absorption throughout the entire thickness of photocatalyst device and better contact of nanostructures that enabled the charge diffusion and charge utilization at redox sites are the reasons for high efficiency. While solar cells require charge carriers to diffuse through long distances of microns, they are utilized locally in an ensemble of particles (of nanometres) for hydrogen generation in photocatalyst thin films; this concept was used effectively in the present work.

1 aNalajala, Naresh1 aPatra, Kshirodra, Kumar1 aBharad, Pradnya, A.1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/why-thin-film-form-photocatalyst-better-particulate-form-direct-solar-hydrogen-conversion01969nas a2200265 4500008004100000022001400041245014300055210006900198260000900267300001600276490000700292520103800299653002001337653001801357653001901375653001301394653001901407100002101426700002801447700001701475700002101492700002901513700003001542856013101572 2020 eng d a1944-824400aCan half-a-monolayer of pt simulate activity like that of bulk pt? solar hydrogen activity demonstration with quasi-artificial leaf device0 aCan halfamonolayer of pt simulate activity like that of bulk pt  cJUL  a30420-304300 v123 a

Pt is the best cocatalyst for hydrogen production. It is also well-known that the surface atomic layer is critical for catalysis. To minimize the Pt content as cocatalyst, herein we report on half-a-monolayer of Pt (0.5 theta(Pt)) decorated on earth-abundant Ni-Cu cocatalyst, which is integrated with a quasiartificial leaf (QuAL) device (TiO2/ZnS/CdS) and demonstrated for efficient solar hydrogen production. For the QuAL, TiO2 is sensitized with ZnS and CdS quantum dots by the SILAR method. The 0.5 theta(Pt)-decorated Ni-Cu shows an onset potential of 0.05 V vs reversible hydrogen electrode for the hydrogen evolution reaction, which is almost similar to that of commercial Pt/C. Photoactivity of the present QuAL device with either bulk Pt or 0.5 theta(Pt)-coated Ni-Cu cocatalyst is, surprisingly, equal. Our findings underscore that a fraction of a monolayer of Pt can enhance the activity of the cocatalyst, and it is worth exploring further for the high activity associated with atomic Pt and other noble metals.

10aartificial leaf10anickel-copper10aPhotocatalysis10aplatinum10aSolar hydrogen1 aBajpai, Himanshu1 aPatra, Kshirodra, Kumar1 aRanjan, Ravi1 aNalajala, Naresh1 aReddy, Kasala, Prabhakar1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/can-half-monolayer-pt-simulate-activity-bulk-pt-solar-hydrogen-activity-demonstration-quasi01740nas a2200241 4500008004100000022001400041245008300055210006900138260000800207300001200215490000600227520098000233653001301213653002201226653001301248653001901261653001701280100001601297700002101313700002001334700003001354856011401384 2020 eng d a2367-198X00aCu-Ni bimetal integrated TiO2 thin film for enhanced solar hydrogen generation0 aCuNi bimetal integrated TiO2 thin film for enhanced solar hydrog cMAY a19005570 v43 a

A series of non-noble Cu-Ni bimetallic catalysts is prepared with different molar proportions of metals. Of these bimetallic catalysts, 1 wt% is subsequently integrated with titania P25. The catalysts are evaluated for solar hydrogen generation under 1 sun condition in both the powder and thin film forms. All the photocatalysts in the thin film exhibit an 8-24 times higher hydrogen yield (HY) compared with the corresponding particulate counterpart. The highest HY (41.7 mmol h(-1) g(-1)) is demonstrated for the photocatalyst Cu-Ni/TiO2 (CNT; 1:1 = Cu:Ni) in the thin film form, which is 24 times higher than that with its powder counterpart (1.75 mmol h(-1) g(-1)) and exceeds the performance of other Cu-Ni/TiO2 compositions. This enhanced activity in the thin film can be ascribed to improved absorption of visible light and an effective separation of photogenerated charge carriers at the interface of Cu-Ni/TiO2 leading to better charge carrier utilization.

10abimetals10aenergy conversion10aHydrogen10aPhotocatalysis10asolar energy1 aTudu, Bijoy1 aNalajala, Naresh1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/cu-ni-bimetal-integrated-tio2-thin-film-enhanced-solar-hydrogen-generation13210nas a2200169 45000080041000002450122000412100069001632600028002324900009002605201253400269100001812803700002612821700001412847700002112861700002612882856013212908 2020 eng d00aPhotocatalytic hydrogen production from H2S using nanostructured CNT blended CdZnS/Fe2O3 thin film on glass substrate0 aPhotocatalytic hydrogen production from H2S using nanostructured bIOP Publishing LtdcMAR0 v14953 a

A co-precipitation method was employed to prepare the CNT blended CdZnS/Fe2O3 photocatalyst. Using the powder photocatalyst, the thin film of CNT blended CdZnS/Fe2O3 photocatalyst over a glass substrate was prepared using the drop-casting method. The obtained thin film was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy-dispersive X-ray analysis (EDAX), photoluminescence (PL), and hydrogen production activity studies in order to obtain information on their structural, morphology, chemical composition, optical and hydrogen production efficiency. The hydrogen production activity of catalyst or effective conversion of H2S into hydrogen (H2) and sulfur (S) using thin-film photocatalyst was evaluated using a simulated sulfide solution. The results showed that 1 mg of CNT blended CdZnS/Fe2O3 catalyst coated as thin film over glass substrate (4.69 cm2) showed the highest hydrogen production value of 3180 μmol h−1g−1; compared to that of 1 mg CNT blended CdZnS/Fe2O3 powder of 2510 μmol h−1g−1. From the above results, it is concluded that the thin film form of photocatlyst produced more hydrogen than the powder form. This is attributed to the effective charge separation and increased specific surface area in thin film photocatalyst.

1 aRaja, Anthony1 aVijayarengan, Preethi1 aPal, Yash1 aNalajala, Naresh1 aGopinath, Chinnakonda uhttps://library.ncl.res.in/content/photocatalytic-hydrogen-production-h2s-using-nanostructured-cnt-blended-cdznsfe2o3-thin-film02461nas a2200253 4500008004100000022001400041245017300055210006900228260000900297300001600306490000600322520151900328653002801847653001801875653001401893653001901907653002501926100002101951700002701972700002301999700002502022700003002047856013002077 2021 eng d a2574-096200aAqueous methanol to formaldehyde and hydrogen on Pd/TiO2 by photocatalysis in direct sunlight: structure dependent activity of nano-Pd and atomic Pt-coated counterparts0 aAqueous methanol to formaldehyde and hydrogen on PdTiO2 by photo cNOV  a13347-133600 v43 aIn the present investigation, facet-controlled Pd nanoparticles with nanocube (Pd-NC) and truncated octahedron (Pd-TO) morphologies, and their counterparts with half-a-monolayer of atomic Pt coated (0.5 theta(Pt)-Pd-NC and 0.5 theta(Pt)-Pd-TO) surfaces were prepared. All of them were characterized and evaluated as cocatalyst after supporting them on commercial titania (P25) (Pd-NC/P25, Pd-TO/P25, 0.5 theta(Pt)-Pd-NC/P25, and 0.5 theta(Pt)-Pd-TO/P25) under direct sunlight and/or one sun conditions for the oxidation of methanol to formaldehyde along with solar hydrogen production. Pd-NC/P25 shows higher activity for hydrogen generation compared to Pd-TO/P25; however, activity reversal occurs with the above cocatalysts, but, after Pt-coating with further enhanced activity. The highest conversion of methanol (0.2 mu mol/h.mg) to 100% selective formaldehyde was observed with 0.5 theta(Pt)-Pd-TO/P25, while other catalysts show significantly lower methanol conversion in the following order: 0.5 theta(Pt)-Pd-TO/P25 > 0.5 theta(Pt)-Pd-NC/P25 > Pd-NC/P25 > Pd-TO/P25. Pt-coated on (111) facets of Pd-TO simulates the activity associated as that of Pt(111) facets and demonstrating the highest and facet dependent activity. The present study is truly in resonance with exploiting the surface properties for heterogeneous catalysis, and highlights that less than a monolayer of Pt is sufficient to simulate the activity as that of bulk Pt. It is worth exploring this concept to other metals and substrates too.10aheterogeneous catalysis10aNanomaterials10aOxidation10aPhotocatalysis10asurface modification1 aNalajala, Naresh1 aSalgaonkar, Kranti, N.1 aChauhan, Inderjeet1 aMekala, Siva, Prasad1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/aqueous-methanol-formaldehyde-and-hydrogen-pdtio2-photocatalysis-direct-sunlight-structure01936nas a2200265 4500008004100000022001400041245013300055210006900188260000800257300001200265490000700277520102200284653002801306653002001334653001901354653001101373653002801384653001901412100002101431700002301452700002101475700001901496700003001515856012501545 2021 eng d a2194-428800aElectronically integrated mesoporous Ag-TiO2 nanocomposite thin films for efficient solar hydrogen production in direct sunlight0 aElectronically integrated mesoporous AgTiO2 nanocomposite thin f cAUG a21003560 v103 a

The synthesis of mesoporous TiO2 by a solution-based assembly process and Ag/TiO2 nanocomposites is provided. The efficacy of Ag/TiO2 nanocomposite as photocatalyst in thin-film form is demonstrated for solar hydrogen generation in sunlight. Integration of Ag with TiO2 dramatically enhanced the H-2 production: with 1 wt% Ag on TiO2 (TiAg-1), the H-2 yield was observed to be 4.59 mmol h(-1) g(-1), which is 2.3 (30) times larger than 0.5 wt% Ag on TiO2. TiAg-1 shows 4.3 times higher activity in film form compared with its powder counterpart. High photocatalytic efficiency is attributed to the surface plasmon resonance effect of Ag, electronic integration of Ag with TiO2, and subsequent valence band broadening, large distribution of Ag nanoparticles and abundant Ag-TiO2 Schottky junctions, and the later minimizes electron-hole recombination. Interparticle mesoporous network increases necking and the high surface area offers easy accessibility of the reactants to a large number of active sites.

10aheterogeneous catalysis10aheterojunctions10aplasmon effect10aSilver10asolar energy conversion10aSolar hydrogen1 aMani, Sunesh, S.1 aRajendran, Sivaraj1 aNalajala, Naresh1 aMathew, Thomas1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/electronically-integrated-mesoporous-ag-tio2-nanocomposite-thin-films-efficient-solar02083nas a2200241 4500008004100000022001400041245012200055210006900177260000800246300001400254490000700268520123300275653002501508653003401533653001501567653002601582653002501608653001401633100003001647700002101677700001901698856012401717 2021 eng d a0959-810300aPolyaryletherketone in energy conversion and storage devices - a highly tailorable material with versatile properties0 aPolyaryletherketone in energy conversion and storage devices a h cAUG a1026-10370 v703 a

Polymers have been a highly useful class of material for the last few decades owing to their ease of bulk production and fabrication. With the myriad of applications in day to day life, they have also found an important role in energy conversion and storage devices, not just as a housing material of the device but with an important role in the energy conversion process. Among the several polymers used in this area, polyaryletherketones (PAEKs) are one of the most versatile materials owing to their easy tailorability. The ether and ketone groups can be introduced in the main polymer chain in several ways to achieve the desired material properties. The main role of a polymer in an energy conversion device is that of a barrier to avoid the mixing of reactants and to selectively transport ions from one electrode to the other to maintain charge neutrality. The polymer membrane finds application in various electrochemical energy conversion devices such as fuel cells, lithium ion batteries, redox flow batteries, supercapacitors etc. The main focus of this work is to briefly review the extent of development in the PAEKs in various energy conversion and storage devices. (c) 2021 Society of Industrial Chemistry.

10aelectrolyte membrane10aenergy conversion and storage10afuel cells10alithium ion batteries10aredox flow batteries10aseparator1 aSaleha, Wasim, Feroze Goo1 aNalajala, Naresh1 aNeergat, Manoj uhttps://library.ncl.res.in/content/polyaryletherketone-energy-conversion-and-storage-devices-highly-tailorable-material02522nas a2200265 4500008004100000022001400041245010300055210006900158260000900227300001600236490000600252520166000258653001501918653001301933653001601946653001701962653000901979653002001988100001602008700002102024700002902045700002002074700003002094856013202124 2021 eng d a2168-048500aRationally designed, efficient, and earth-abundant Ni-Fe cocatalysts for solar hydrogen generation0 aRationally designed efficient and earthabundant NiFe cocatalysts cOCT  a13915-139250 v93 aDeveloping highly efficient and affordable catalysts for solar hydrogen (H-2) generation is crucial, and employing a cocatalyst from earth-abundant elements has a critical role to play. In this context, different compositions of earth-abundant Ni-Fe alloy (1:1, 1:3, and 3:1) have been prepared by hydrothermal method; subsequently, 1 wt % of these Ni-Fe cocatalysts were integrated with TiO2-P25 and thoroughly characterized. The resultant catalysts have been evaluated for solar H-2 production, in powder and thin film forms, under one sun condition and in direct sunlight. Interestingly, all the catalysts in the thin film form exhibit superior hydrogen yield (HY), up to 27 times higher activity than its powder counterpart. Among the photocatalysts, Ni-Fe/TiO2 (3:1 = Ni/Fe; NFT31) composition exhibits the best HY in thin film (8.27 mmol.h(-1).g(-1)) and exceeds all other compositions of catalyst. It is also to be reported that HY measured for the powder form with 1 mg shows 3-17 times higher activity than that measured with 25 mg. This is mainly attributed to effective solar light absorption with a smaller amount of photocatalyst either spread over large area in a thin film form or well-dispersed in suspension forms. Furthermore, the enhanced activity obtained with Ni-Fe/TiO2 photocatalysts is also ascribed to strong electronic integration of Ni-Fe cocatalyst with TiO2 and higher performance obtained with a thin film is attributed to increased charge carrier generation and subsequent charge separation and effective utilization. A decrease in work function of TiO2 by 0.6 eV was observed after its integration with cocatalyst in NFT31.10aCocatalyst10aHydrogen10aNi-Fe alloy10asolar energy10aTiO210awater splitting1 aTudu, Bijoy1 aNalajala, Naresh1 aReddy, Kasala, Prabhakar1 aSaikia, Pranjal1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/rationally-designed-efficient-and-earth-abundant-ni-fe-cocatalysts-solar-hydrogen-generation02474nas a2200157 4500008004100000022001400041245011900055210006900174260000800243300001400251490000600265520186600271100003002137700002102167856012802188 2021 eng d a2050-748800aScalable and thin film approach for solar hydrogen generation: a review on enhanced photocatalytic water splitting0 aScalable and thin film approach for solar hydrogen generation a  cJAN a1353-13710 v93 a

Although nearly five decades of efforts have gone into solar water splitting (SWS), still success eludes and there is no big breakthrough till date. While huge importance is given either individually or concurrently to the three fundamental steps, namely, light absorption, charge carrier separation and diffusion and charge utilization at redox sites, many aspects that are practically helpful to improve the efficiency are not widely discussed and practised. Nonetheless, by adopting a number of small, but significant changes, solar hydrogen production can be enhanced. The present review discusses such different approaches employed for photocatalytic water splitting reported in the literature. For example, an increase of up to two orders of magnitude in solar hydrogen generation was observed with a film form compared to the particulate form of the same catalyst. Discussion on various approaches of enhanced hydrogen production under sunlight and one sun conditions is the main focus of this review, in particular with thin-film forms. The merits and demerits of thin film and particulate methods, respectively, are addressed in detail. Potential methods and successful stories on scalability are also discussed in the present review. In contrast to charge collection over a long distance in solar cell-based methods, a film-based method discussed shows that the local charge utilisation at a zero applied potential is an attractive feature for SWS. A comparison is provided between the PEC-WS and SWS for solar hydrogen generation, and how far we are from the reality to produce solar hydrogen on an industrial scale. We believe the presently practised diverse evaluation efforts may be truncated to fewer methods such as film-based evaluation and in a focussed manner to tackle the SWS issue towards sustainable production of solar hydrogen.

1 aGopinath, Chinnakonda, S.1 aNalajala, Naresh uhttps://library.ncl.res.in/content/scalable-and-thin-film-approach-solar-hydrogen-generation-review-enhanced-photocatalytic02917nas a2200229 4500008004100000022001400041245015400055210006900209260000900278300001600287490000700303520206700310100002702377700002102404700002302425700002102448700002302469700002002492700001802512700003002530856012702560 2023 eng d a2050-748800aBaby step in assembling and integrating the components of an artificial photosynthesis device with forced heterojunctions towards improved efficiency0 aBaby step in assembling and integrating the components of an art cJUL  a15168-151820 v113 a

How to achieve unassisted, economical, scalable, and sustainable artificial photosynthesis for liquid fuels/products with improved solar-to-fuel efficiency (STFE) to address a carbon-neutral economy remains a big question. To a large degree, the extent of charge separation at heterojunction interfaces and charge utilization determine the STFE. Towards this, BiVO3 is assembled from ionic-precursors into TiO2 pores, and integrated structurally and electronically with TiO2 on calcination as BiVO4 quantum dots (BVQDs). BVQDs in TiO2 (BVT) pores lead to an all-inorganic system with a sub-quadrillion number of heterojunctions in a 1 cm(2) device (contains similar to 25 mu g of BiVO4 (similar to 2.5 wt%) in the nanopores of similar to 975 mu g of TiO2 (similar to 97.5 wt%)) and facilitate artificial photosynthesis. We demonstrate 31-38% STFE with a photon to chemical conversion turn over frequency (ToF(P2C)) of 2.73 s(-1) with a 1 cm(2) wireless BiVO4-TiO2 artificial leaf (BVT-AL) device for HCHO and CH3OH. The sequential nature of CO2 reduction to HCHO and then to CH3OH is evident from the reaction results. (CO2)-C-13 isotopic labeling experiments confirm that the input CO2 is the source for product formation. A large increase in the photocurrent density and incident photon-to-current efficiency (IPCE) of BVT, over 100% for the BiVO4 photoanode in visible light, demonstrates and supports efficient visible light absorption, charge separation and migration to the redox sites. A device has been demonstrated to show sustainable activity in direct sunlight, and addresses scalability from 1 to 9 cm(2). Assuming no change (50% decrease) in the STFE, a 6.74 m(2) device is expected to convert 1 (0.5) kg h(-1) CO2 into C1-oxygenates in sunlight. DFT calculations carried out with anatase TiO2 (101) and BiVO4 (121) interfaces support many of the experimental findings, including electron flow from the latter to the former, and interaction of the oxygen of TiO2 with BiVO4 and vice versa at the interface towards forced heterojunctions.

1 aSalgaonkar, Kranti, N.1 aBajpai, Himanshu1 aMhamane, Nitin, B.1 aNalajala, Naresh1 aChauhan, Inderjeet1 aThakkar, Kavita1 aJoshi, Kavita1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/baby-step-assembling-and-integrating-components-artificial-photosynthesis-device-forced01482nas a2200277 4500008004100000022001400041245012100055210006900176260000800245300001200253490000700265520056300272653001000835653001400845653001900859653002000878100002400898700002000922700001900942700001700961700002000978700002100998700003001019700002301049856013201072 2023 eng d a0909-049500aPhotocatalytic setup for in situ and operando ambient-pressure X-ray photoelectron spectroscopy at MAX IV Laboratory0 aPhotocatalytic setup for in situ and operando ambientpressure Xr cMAY a613-6190 v303 a

The Ambient-Pressure X-ray Photoelectron Spectroscopy (APXPS) endstation at the SPECIES beamline at MAX IV Laboratory has been improved. The latest upgrades help in performing photo-assisted experiments under operando conditions in the mbar pressure range using gas and vapour mixtures whilst also reducing beam damage to the sample caused by X-ray irradiation. This article reports on endstation upgrades for APXPS and examples of scientific cases of in situ photocatalysis, photoreduction and photo-assisted atomic layer deposition (photo-ALD).

10aAPXPS10aphoto-ALD10aPhotocatalysis10asolar simulator1 aKlyushin, Alexander1 aGhosalya, Manoj1 aKokkonen, Esko1 aEads, Calley1 aJones, Rosemary1 aNalajala, Naresh1 aGopinath, Chinnakonda, S.1 aUrpelainen, Samuli uhttps://library.ncl.res.in/content/photocatalytic-setup-situ-and-operando-ambient-pressure-x-ray-photoelectron-spectroscopy-max02861nas a2200241 4500008004100000022001400041245018000055210006900235260000900304300001600313490000700329520193900336100002602275700002002301700002602321700001702347700003002364700002602394700002102420700001902441700003302460856012602493 2023 eng d a1463-907600aPossible handle for broadening the catalysis regime towards low temperatures: proof of concept and mechanistic studies with CO oxidation on surface modified Pd-TiO20 aPossible handle for broadening the catalysis regime towards low  cAUG  a22040-220540 v253 a

The present work demonstrates the effect of temperature-dependent surface modification (SM) treatment and its influence in broadening the catalysis regime with Pd-TiO2 catalysts prepared by various methods. Due to SM induced changes, a shift in the onset of CO oxidation activity as well as broadening of the oxidation catalysis regime by 30 to 65 K to lower temperatures is observed compared to the temperature required for virgin counterparts. SM carried out at 523 K for Pd-Photo-TiO2 exhibits the lowest onset (10% CO2 production - T-10) and T-100 for CO oxidation at 360 and 392 K, respectively, while its virgin counterpart shows T-10 and T-100 at 393 and 433 K, respectively. The SMd Pd-TiO2 catalysts were investigated using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS) and atomic force microscopy (AFM). It is observed that diffusion of atomic oxygen into Pd-subsurfaces leads to SM and changes the nature of the surface significantly. These changes are demonstrated by work function (& phi;), surface potential, catalytic activity, and correlation among them. UPS results demonstrate the maximum increase in & phi; by 0.5 eV for Pd-Photo-TiO2 after SM, compared to all other catalysts. XPS study shows a moderate to severe change in the oxidation states of Pd due to atomic oxygen diffusion into the subsurface layers of Pd. Kelvin probe force microscopy (KPFM) study also reveals corroborating evidence that the surface potential increases linearly with increasing temperature deployed for SM up to 523 K, followed by a marginal decrease at 573 K. The & phi; measured by KPFM and UPS shows a similar trend and correlates well with the changes in catalysis observed. Our results indicate that there is a strong correlation between surface physical and chemical properties, and & phi; changes could be considered as a global marker for chemical reactivity.

1 aMhamane, Nitin, B. B.1 aPanchal, Suresh1 aKolekar, Sadhu, K. K.1 aRanjan, Ravi1 aSalgaonkar, Kranti, N. N.1 aBurange, Anand, S. S.1 aNalajala, Naresh1 aDatar, Suwarna1 aGopinath, Chinnakonda, S. S. uhttps://library.ncl.res.in/content/possible-handle-broadening-catalysis-regime-towards-low-temperatures-proof-concept-and02213nas a2200241 4500008004100000022001400041245018400055210006900239260000800308490000700316520131500323653002201638653001801660653001401678653001901692653001901711100002701730700002101757700002101778700002001799700003001819856012201849 2023 eng d a1861-472800aSelective and generic photocatalytic oxidation of alcohol with Pd-TiO2 thin films: butanols to butanal/butanone with different morphologies of Pd and 0.5 theta(Pt)-Pd counterparts0 aSelective and generic photocatalytic oxidation of alcohol with P cMAR0 v183 a

The present study reports on the photocatalytic oxidation of butanols to butanal/butanone using thin film form of facet-dependent nano-Pd supported on commercial TiO2 under one-sun condition and demonstrates the generic nature. Pd-nanocube (Pd-NC(100)), Pd-truncated octahedron (Pd-TO (100) and (111)), polycrystalline (Pd-PC), and their counterparts with half-a-monolayer Pt-coated on Pd (0.5 theta(Pt)-Pd)) have been used as co-catalyst. A potentially scalable thin film form of Pd/TiO2 photocatalyst, prepared by drop-casting method, has been employed to study oxidation of n-butanol, 2-butanol, and iso-butanol to corresponding aldehyde/ketone. 100% selectivity is demonstrated to respective aldehyde/ketone with any catalyst used in the present study with varying degree of butanols conversion by NMR. 0.5 theta(Pt)-Pd-TO/TiO2 shows the highest conversion of 2-butanol to butanone (13.6% in 4 h). Continuous 10 h of reaction with the most active 0.5 theta(Pt)-Pd-TO/P25 catalyst demonstrates 31% conversion of 2-butanol to butanone, and catalyst recyclability has been demonstrated. The present protocol can be scalable to large scales to maximize the conversion in direct sunlight. Due to its generic nature, the current method can also be applied to many other alcohols and substrate molecules.

10aenergy conversion10aNanomaterials10aOxidation10aPhotocatalysis10aSustainability1 aSalgaonkar, Kranti, N.1 aKale, Sandip, R.1 aNalajala, Naresh1 aMansuri, Sayana1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/selective-and-generic-photocatalytic-oxidation-alcohol-pd-tio2-thin-films-butanols11736nas a2200181 45000080041000002450147000412100069001882600008002573000011002654900007002765201101800283100002611301700002511327700002111352700002111373700003011394856013011424 2025 eng d00aThin-film approach for scalability and enhancement of solar hydrogen production with CNT integrated Ce-doped-TiO2 composite in direct sunlight0 aThinfilm approach for scalability and enhancement of solar hydro cSEP a1001150 v103 a

Solar hydrogen production by photocatalysis has long been considered as an important energy option. Whichever photocatalyst succeeds, methods should be available to scale-up in a most sustainable and cost-effective manner, and the present work addresses this specific issue. In the present study, Ce-doped in the TiO2 lattice (Ce-TiO2) and the same integrated with CNT (CNT-Ce-TiO2; (CCT)) composite was synthesized and characterized. Current study demonstrates the synergistic integration of Ce-TiO₂ as a light absorber and charge generator with CNTs as efficient charge separation at heterojunctions as well as charge transporter in a thin-film configuration (lab-scale (4.7 cm2), bench-scale (500 cm2)). Improved H2 generation under direct sunlight demonstrated in thin film form, than in particulate suspension, is attributed to efficient light absorption, particularly for electron-hole pair separation and their dispersion to redox sites. Additionally, the role of the binder is highlighted for improving H2 yield and the sustainability of the thin-film form of photocatalyst. ∼200 mg (1 g) CCT coated over 500 cm2 (2500 cm2) photocatalyst produced 21.6 mmol/h (102 mmol/h) H2 in sunlight. Present results provides a proof of concept that the thin film form of photocatalyst displays, at least 10 times, higher H2 yield than its powder counterpart, depending on the measurement conditions. A non-linear enhancement in H2 yield with small and large area thin-film indicates complex underlying factors and highlights the scope for further improvements.

1 aVijayarengan, Preethi1 aMaria, Anthony, Raja1 aAshadevi, K., S.1 aNalajala, Naresh1 aGopinath, Chinnakonda, S. uhttps://library.ncl.res.in/content/thin-film-approach-scalability-and-enhancement-solar-hydrogen-production-cnt-integrated-ce02989nas 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

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 (>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.

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