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1.
Langmuir ; 40(21): 10835-10846, 2024 May 28.
Article in English | MEDLINE | ID: mdl-38740571

ABSTRACT

The advent of two-dimensional layered materials has bolstered the development of catalytic endeavors for energy conversion and storage. MXenes (transition metal carbides/nitrides) have already consolidated their candidature in the past decade due to their enhanced compositional and structural tunabilities through surface modifications. Perseverant research in engineering MXene based materials has led to the inception of MBenes (transition metal borides) as promising catalytic systems for energy-driven operations. Physicochemical superiorities of MBenes such as escalated conductivity and hydrophilicity, unique surface and geometrical domains, and higher stability and modulus of elasticity provide the reaction-friendly milieu to exploit these materials. Nevertheless, the research on MBenes is embryonic and requires the thorough realization of their scientific significance. Herein, we aim to discuss the advancements, challenges, and outlooks of MBenes with respect to their energy conversion HER, CO2RR, and NRR applications.

2.
Langmuir ; 40(20): 10414-10432, 2024 May 21.
Article in English | MEDLINE | ID: mdl-38728278

ABSTRACT

To mimic the carbon cycle at a kinetically rapid pace, the sustainable conversion of omnipresent CO2 to value-added chemical feedstock and hydrocarbon fuels implies a remarkable prototype for utilizing released CO2. Porous organic polymers (POPs) have been recognized as remarkable catalytic systems for achieving large-scale applicability in energy-driven processes. POPs offer mesoporous characteristics, higher surface area, and superior optoelectronic properties that lead to their relatively advanced activity and selectivity for CO2 conversion. In comparison to the metal organic frameworks, POPs exhibit an enhanced tendency toward membrane formation, which governs their excellent stability with regard to remarkable ultrathinness and tailored pore channels. The structural ascendancy of POPs can be effectively utilized to develop cost-effective catalytic supports for energy conversion processes to leapfrog over conventional noble metal catalysts that have nonlinear techno-economic equilibrium. Herein, we precisely surveyed the functionality of POPs from scratch, classified it, and provided a critical commentary of its current methodological advancements and photo/electrochemical achievements in the CO2 reduction reaction.

3.
Inorg Chem ; 63(1): 304-315, 2024 Jan 08.
Article in English | MEDLINE | ID: mdl-38146688

ABSTRACT

The simultaneous realization of sustainable energy and gas sensors dealing with the emission of pollutants is indispensable as the former thrives on the minimization of the latter. However, there is a dearth of multifunctional nanocatalysts in the literature. This ascertains the importance of multifunctional semiconductors which can be utilized in H2 generation via overall water splitting and in the gas sensing of global pollutants such as NH3. MoO3-decorated TiO2 Z-scheme heterostructures exceptionally escalate the photochemical and photo/electrochemical H2 evolution performance and gas sensing response of TiO2 owing to the synergistic relationship between TiO2 and MoO3. Extensive structural, morphological, and optical characterizations, theoretical studies, and XPS results were exploited to develop a mechanistic framework of photochemical H2 evolution. The photochemical response of the optimum TiO2-MoO3 composition (20 wt % MoO3-TiO2) was found to be nearly 12- and 20-fold superior to the pristine TiO2 and MoO3 photocatalysts, respectively, with the remarkable H2 evolution rate of 9.18 mmol/g/h and AQY of 36.02%. In addition, 20 wt % MoO3-TiO2 also showed advanced photo/electrochemical efficiency with 0.61/0.7 V overpotential values toward HER due to the higher electrochemically active surface area and Tafel slope as low as 65 mV/dec. The gas sensing response of 20 wt % MoO3-TiO2 toward NH3 gas turned out to be 2.5-fold higher than that of the pristine TiO2 gas sensor.

4.
Langmuir ; 39(36): 12692-12706, 2023 Sep 12.
Article in English | MEDLINE | ID: mdl-37639496

ABSTRACT

Highly efficient Z-scheme MoO3-SrTiO3 heterostructured nanocatalytic systems were engineered via a sol-gel chemical route and exploited in green H2 energy synthesis via overall water splitting. The optical and electronic investigations corroborated the enhancement of the optoelectronic properties of SrTiO3 after the incorporation of MoO3. Emergence of the interfacial charge transfer between SrTiO3 and MoO3 is the driving force, which synergistically triggered the catalytic efficiency of MoO3-SrTiO3 heterostructures. The substitution of Ti4+ by Mo6+ ions led to the suppression of Ti3+ mid-gap states, as the potential involved in the Mo6+/Mo5+ reduction is higher than that in Ti4+/Ti3+. Theoretical studies were employed in order to comprehend the mechanism behind the advancement in the catalytic activity of MoO3-SrTiO3 porous heterostructures, which also possessed a higher surface area. 2% MoO3-SrTiO3 exhibited the optimum catalytic response toward H2 evolution via photochemical, electrochemical, and photo-electrochemical water splitting. 2% MoO3-SrTiO3 evolved H2 at the fourfold higher rate than SrTiO3 with phenomenal 16.06% AQY during photochemical water splitting and photo-degraded MB dye at nearly 88% against the 42% degradation in SrTiO3-led photocatalysis. Electrochemical and photo-electrochemical investigations also manifested the superiority of 2% MoO3-SrTiO3 toward HER, as it exhibited accelerated current and photocurrent densities of 25.02 and 27.45 mA/cm2, respectively, at the 1 V potential. EIS studies demonstrated the improved charge separation efficiency of MoO3-SrTiO3 heterostructures. This work highlights the multi-dimensional approach of obtaining green H2 energy as the sustainable energy source using MoO3@SrTiO3 heterostructures.

5.
Nanotechnology ; 33(35)2022 Jun 14.
Article in English | MEDLINE | ID: mdl-35580560

ABSTRACT

Semiconductor photocatalysis has gained considerable attention in recent years due to their enabling nature to convert solar energy into fuels of renewable hydrocarbon. However, many of them suffer from some drawbacks like the inability to visible light irradiation and wide band gaps. Herein, we have synthesized monophasic strontium (Sr) doped SnO2nanoparticles by a cost-effective and environmental friendly hydrothermal method. As-synthesized nanoparticles showed rutile crystalline structure with irregular and rough cubical shape and no other elemental impurities. Sr-doped SnO2nanoparticles show a constant decrease in bandgap with increasing dopant concentration, which is estimated for excellent photocatalytic activity. The photocatalytic water splitting of as-prepared Sr-doped SnO2nanoparticles for H2generation shows a large influence of the increasing dopant concentration related to the narrowing bandgap on H2generation rate. Hence, the tunable bandgap with adjusted dopant concentration indicates that band gap tuning through doping for produced nanostructures may open up a new opportunities for photocatalytic and other optoelectronic applications.

6.
ACS Omega ; 7(16): 14138-14147, 2022 Apr 26.
Article in English | MEDLINE | ID: mdl-35559165

ABSTRACT

Cr-doped SnO2 nanostructures with a dopant concentration ranging from 1 to 5% have been successfully prepared using low-temperature modified solvothermal synthesis. The as-prepared nanoparticles showed a rutile tetragonal structure with a rough undefined morphology having no other elemental impurities. The particle shape and size, band gap, and specific surface area of the samples were investigated by scanning electron microscopy, transmission electron microscopy (TEM), high-resolution TEM, UV-visible diffused reflectance spectroscopy, and Brunauer-Emmett-Teller surface area studies. The optical band gap was found in the range of 3.23-3.67 eV and the specific surface area was in the range of 108-225 m2/g, which contributes to the significantly enhanced photocatalytic and electrochemical performance. Photocatalytic H2 generation of as-prepared Cr-doped SnO2 nanostructures showed improved effect of the increasing dopant concentration with narrowing of the band gap. Electrochemical water-splitting studies also stressed upon the superiority of Cr-doped SnO2 nanostructures over pristine SnO2 toward hydrogen evolution reaction and oxygen evolution reaction responses.

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