Nanoengineered Cobalt Electrocatalyst for Alkaline Oxygen Evolution Reaction.

The alkaline oxygen evolution reaction (OER) remains a bottleneck in green hydrogen production owing to its slow reaction kinetics and low catalytic efficiencies of earth abundant electrocatalysts in the alkaline OER reaction. This study investigates the OER performance of hierarchically porous cobalt electrocatalysts synthesized using the dynamic hydrogen bubble templating (DHBT) method. Characterization studies revealed that electrocatalysts synthesized under optimized conditions using the DHBT method consisted of cobalt nanosheets, and hierarchical porosity with macropores distributed in a honeycomb network and mesopores distributed between cobalt nanosheets. Moreover, X-ray photoelectron spectroscopy studies revealed the presence of Co(OH)2 as the predominant surface cobalt species while Raman studies revealed the presence of the cubic Co3O4 phase in the synthesized electrocatalysts. The best performing electrocatalyst required only 360 mV of overpotential to initiate a current density of 10 mA cm-2, exhibited a Tafel slope of 37 mV dec-1, and stable OER activity over 24 h. The DHBT method offers a facile, low cost and rapid synthesis approach for preparation for highly efficient cobalt electrocatalysts.

Surface functionalized 3D printed metal structures as next generation recyclable SERS substrates.

Combining the design flexibility and rapid prototyping capabilities of additive manufacturing with photocatalytic and plasmonic functionalities is promising for the development of next-generation SERS applications such as point of care diagnostics and in situ monitoring of chemical reactions in fuels and chemical processing. Laser powder bed fusion (LPBF) is a well-matured additive manufacturing technique which generates metallic structures through localised melting and joining of metal powders using a laser. LPBF reduces material wastage during manufacturing, is applicable to a wide range of metals and alloys, and allows printing of complex internal structures. This feature article elaborates the use of soot templating, chemical vapour deposition and electroless plating techniques for grafting plasmonic and semiconductor nanoparticles on the surface of LPBF manufactured metallic substrates. The capability to fabricate different types of intricate metallic lattices using additive manufacturing is demonstrated and technical challenges in their adequate functionalization are elaborated. The developed methodology allows tailoring of the substrate structure, composition, morphology, plasmonic and photocatalytic activities and thus unveils a new class of recyclable SERS substrates.

Smart Nanozymes for Cancer Therapy: The Next Frontier in Oncology.

Nanomaterials that mimic the catalytic activity of natural enzymes in the complex biological environment of the human body are called nanozymes. Recently, nanozyme systems have been reported with diagnostic, imaging, and/or therapeutic capabilities. Smart nanozymes strategically exploit the tumor microenvironment (TME) by the in situ generation of reactive species or by the modulation of the TME itself to result in effective cancer therapy. This topical review focuses on such smart nanozymes for cancer diagnosis, and therapy modalities with enhanced therapeutic effects. The dominant factors that guide the rational design and synthesis of nanozymes for cancer therapy include an understanding of the dynamic TME, structure-activity relationships, surface chemistry for imparting selectivity, and site-specific therapy, and stimulus-responsive modulation of nanozyme activity. This article presents a comprehensive analysis of the subject including the diverse catalytic mechanisms of different types of nanozyme systems, an overview of the TME, cancer diagnosis, and synergistic cancer therapies. The strategic application of nanozymes in cancer treatment can well be a game changer in future oncology. Moreover, recent developments may pave the way for the deployment of nanozyme therapy into other complex healthcare challenges, such as genetic diseases, immune disorders, and ageing.

Readily tunable surface plasmon resonances in gold nanoring arrays fabricated using lateral electrodeposition.

Generation and fine-tuning of surface plasmon resonances is a prerequstite for several established and emerging applications such as photovoltaics, photocatalysis, photothermal therapy, surface-enhanced spectroscopy, sensing, superlensing and lasing. We present a low-cost and scalable lateral electrodeposition method for fabrication of high aspect ratio gold nanoring arrays that exhibit multiple surface plasmon resonances in the visible to near-infrared region. Nickel disc arrays of 2 µm size were initially fabricated using maskless lithography and e-beam evaporation. Selective electrodeposition of gold on the lateral surfaces of nickel disc arrays was achieved using a 50 nm SiO2 film as an insulating mask. Growing from miniscule 100 nm wide lateral surfaces of nickel discs, nanorings with height up to 1084 nm could be obtained with their thickness and aspect ratio governed by the duration of electrodeposition. Facile tuning of the number of plasmon resonances, their resonant wavelength and relative intensity is demonstrated with applications in plasmon mediated photocatalysis and surface-enhanced Raman scattering.

Mesoporous superacid catalysts for valorisation of refinery naphtha stream.

In the current petroleum refining scenario, many refineries end up with surplus naphtha which is either absorbed into the gasoline pool or exported at unattractive prices. Therefore, several options for naphtha valorisation are currently being explored. The usage of Liquified Petroleum Gas (LPG) as a fuel in heating appliances, cooking equipment and automobiles is rapidly increasing. The high specific calorific value, high octane number, clean and efficient combustion of LPG distinguish it as an extremely promising fuel of the future. In the current work, tungstophosphoric acid (TPA) supported on four different mesoporous silica supports were investigated as mesoporous superacids for hydroconversion of refinery naphtha using n-heptane as a model feedstock. The varied levels of interactions of prepared mesoporous silica with tungstophosphoric acid catalysts were observed to have a prominent effect on the strength of the acid sites generated on silica surfaces and as a result affected heptane hydroconversion activity and selectivity of isomerized and cracked products. Interestingly, activity could be tuned towards selective cracking or isomerization-cracking by selection of a suitable topology of mesoporous silica. Hexagonal Mesoporous Silica (HMS) and plugged SBA-15 supported TPA catalysts demonstrated high n-heptane conversion activity and isomerization selectivity whereas KIT-6 and SBA-15 supported TPA catalysts demonstrated high cracking selectivity to LPG.