Empowering the Water Oxidation Activity of the Bimetallic Metal-Organic Framework by Annexing Gold Nanoparticles over the Catalytic Surface.

Electrocatalytic water splitting to an anodic oxygen evolution reaction (OER) and a cathodic hydrogen evolution reaction (HER) is believed to be the most important application for sustainable hydrogen generation. Being a four-electron, four-proton transfer process, the OER plays the main obstacle for the same. Therefore, designing an effective electrocatalyst to minimize the activation energy barrier for the OER is a research topic of prime importance. The metal-organic framework (MOF) with a highly porous network is considered an appropriate candidate for the OER in alkaline conditions. Apart from several MOFs, the bimetallic one has an advantageous electrocatalytic performance due to the synergistic electronic interaction between two metal ions. However, most bimetallic MOFs have an obstacle to electrocatalytic application due to their low conductive nature, and therefore, they possess a barrier for charge transfer kinetics at the interface. Surface functionalization via various nanoparticles (NPs) is believed to be the most effective strategy for nullifying the conductive issue. In this work, we have designed a CoNi-based bimetallic MOF that was surface-functionalized by Au NPs (Au@CoNi-Bpy-BTC) for the OER under alkaline conditions. Au@CoNi-Bpy-BTC required an overpotential of just 330 mV, which is 56 mV lower as compared to the pristine MOF. Impedance analysis confirms an improved conductivity and charge transfer at the interface, where Au@CoNi-Bpy-BTC possesses a lower Rct value than CoNi-Bpy-BTC materials. Moreover, the Au-decorated MOF shows an 8.5 times increase in the TOF value compared to the pristine MOF. Therefore, this noble strategy toward the surface functionalization of MOFs via noble metal NPs is believed to be the most effective strategy for developing effective electrocatalysts for electrocatalytic application in energy-related fields. Overall, this report displays an exceptional correlation between the decorated NPs over the MOF surface, which can regulate the OER activity, as confirmed by experimental analysis.

Decoration of Au Nanoparticles over LaFeO3: A High Performance Electrocatalyst for Total Water Splitting.

Electrocatalytic water splitting has emerged as a promising approach for clean and sustainable hydrogen production. The LaFeO3 perovskite structure exhibits intriguing properties such as mixed ionic-electronic conductivity, high stability, and abundant active sites for electrocatalysis. However, its OER and HER activities are limited by the sluggish kinetics of these reactions. To overcome this limitation, Au nanoparticles (NPs) are decorated onto the surface of LaFeO3 through a facile synthesis method. The Au NPs on the LaFeO3 surface provide additional active sites for water splitting reactions, promoting the adsorption and activation of water molecules. The presence of Au enhances the charge transfer kinetics via the heterostructure between Au NPs and LaFeO3 and facilitates electron transport during the OER and HER process. The catalyst requires only 318 and 199 mV as overpotential to attain a 50 mA cm-2 current density in 1 M KOH solution. Our results demonstrate that the Au@LaFeO3 catalyst exhibits significantly improved electrocatalytic activity compared to pure LaFeO3 and other catalysts reported in the literature. The enhanced performance is attributed due to the synergistic effects between Au NPs and LaFeO3, including an increased surface area, improved conductivity, and optimized surface energetics. Overall, the Au-decorated LaFeO3 catalyst presents a promising candidate for efficient electrocatalytic water splitting, providing a pathway for sustainable hydrogen production. The insights gained from this study contribute to the development of advanced catalysts for renewable energy technologies and pave the way for future research in the field of electrochemical water splitting.

Stabilization of Ru NPs over 3D LaCrO3 Nanostructures for High-Performance HER Catalysts in Acidic Media.

Hydrogen is considered as one of the best alternatives to carbon-based fossil fuels as energy sources. Electrocatalytic water splitting is one of the finest and eco-friendly methods for the production of hydrogen as compared to all other methods such as stream reforming carbon, hydrolysis of metal hydrides, etc. However, the sluggish kinetics on both the half-cell reactions limits the large-scale production of hydrogen. Hence, to overcome such kind of kinetic issues, designing a catalyst with characteristics of low overpotential and high stability is a matter of prime importance for the research community. Perovskite oxides are one of the well-documented materials for their excellent electrocatalytic water oxidation activity. But because of the lack of a proper proton adsorption site, these materials are unable to show proper hydrogen evolution reaction (HER) activity. Several strategies have been adopted for improving the HER activity of perovskite materials like cation doping, nanostructuring, etc. Here in this work, we prepared a shape-selective LaCrO3 (LCO) material. To enhance the electrocatalytic activity, we decorated the LCO with Ru nanoparticles via a hydrothermal method with different concentrations of Ru (Ru@LaCrO3), coined LCOn (n = 1-2.5). The as-synthesized RLCO2.5 showed the highest HER activity by demanding a low overpotential of 150 mV, whereas bare LCO demanded a higher overpotential of 364 mV to reach the benchmark current density of 10 mA/cm2. Also, RLCO2.5 showed a very low Rct value of 15.8 Ω and followed the facile kinetics with a lower Tafel value of 101 mV/dec. It also showed excellent stability over 55 h at a current density of 10 mA/cm2 in chronoamperometry studies. Acceleration degradation studies of RLCO2.5 showed comparably good activity with a small hike in overpotential toward HER. Hence, RLCO-based materials are highly helpful to develop efficient electrocatalysts to produce hydrogen in a large scale.

Photo-Electrochemical Water Splitting Behavior of Directionally Aligned CdSe Quantum Dots on Copper(II) Benzene-1,3,5-Tricarboxylate Metal-Organic Frameworks (MOFs).

Herein, a facile synthesis protocol for the development of directional alignment of CdSe quantum dots (QDs) on the surface of Copper benzene-1, 3, 5-tricarboxylate (CuBTC) metal-organic frameworks (MOFs) was proposed. The sensitization of CdSe QDs with MOFs offered enhancement of light-harvesting properties in the visible region of the solar spectrum due to the broad absorption band of CdSe QDs. As a photo-anode, it has generated current density of ˜20 mA/cm² at 1.70 V (vs. Reversible hydrogen electrode (RHE)) during the photo-electrochemical water splitting in 1 M Na2S electrolyte. The present investigation demonstrates the directional attachment of CdSe QDs on CuBTC is beneficial in facilitating light-harvesting and photo-electrochemical properties of CuBTC MOFs.

Role of Surface Oxygen Vacancies and Lanthanide Contraction Phenomenon of Ln(OH)3 (Ln = La, Pr, and Nd) in Sulfide-Mediated Photoelectrochemical Water Splitting.

Herein, we report the role of surface oxygen vacancies and lanthanide contraction phenomenon on HS- anion adsorption and desorption in the sulfide-mediated photoelectrochemical water splitting of Ln(OH)3 (Ln = La, Pr, and Nd). The Ln(OH)3 were synthesized via a solvothermal route using ethylenediamine as the solvent. The surface defects are characterized by Raman, X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), and high-resolution transmission electron microscopy analyses. The photoelectrochemical water-splitting behavior of Ln(OH)3 enriched with surface oxygen vacancies has been examined in a 1 M Na2S solution under illumination conditions. La(OH)3 exhibited a highly stable and saturated current density of ∼26 mA/cm2 at 0.8 V (vs Ag/AgCl). Similarly, the hydroxides of Pr and Nd demonstrated current densities of 18 and 14 mA/cm2, respectively, at 0.8 V (vs Ag/AgCl). A reduction trend in the saturated current densities from La to Nd indicates the lanthanide contraction phenomenon, where the basicity decreases in the same order. The results also demonstrate that the surface adsorption of the HS- anion in the active sites of the surface oxygen vacancies played a vital role in enhancing the photoelectrochemical water-splitting behavior of Ln(OH)3. The stability of Ln(OH)3 was examined after 4 h of chronoamperometry studies at 0.8 V (vs Ag/AgCl) and analyzed using X-ray diffraction, Fourier transform infrared, Raman, and EPR and XPS analyses. The results show that the Ln(OH)3 exhibited excellent stability by demonstrating their phase purity after photoelectrochemical water splitting. We propose Ln(OH)3 as highly stable photoelectrochemical water-splitting catalysts in highly concentrated sulfide-based electrolytes and anticipate Ln(OH)3 systems to be explored in a major scale for the production of H2 as an ecofriendly process.

Enhanced Photoelectrochemical Water Splitting Behaviour of Tuned Band Gap CdSe QDs Sensitized LaB6.

We report the fabrication of tuned band gap quantum dots sensitized LaB6 hybrid nanostructures and their application as a photoanode for photoelectrochemical water splitting. The lanthanum hexaboride (LaB6) obtained by molten salt electrolysis method is sensitized with different sized CdSe quantum dots, which form a multiple-level hierarchical heterostructure and such design enhance the light absorption and charge carrier separation, which in turn showed higher photocurrent density compared to that of pristine LaB6. When LaB6 is sensitized with CdSe quantum dots of different band gaps, which have the absorption in the green and red (530 and 605 nm) regions in visible light, developed a ten times higher photocurrent density (11.0 mA cm(−2)) compared to that of pristine LaB6 (0.5 mA cm(−2) at 0.75 V vs. Ag/AgCl) in 1 M Na2S electrolyte under illumination. These results prove that the tuned band gap quantum dots sensitized LaB6 heterostructures are an ideal candidate for a photoanode in solar water splitting applications.

Heterostructured Au NPs/CdS/LaBTC MOFs Photoanode for Efficient Photoelectrochemical Water Splitting: Stability Enhancement via CdSe QDs to 2D-CdS Nanosheets Transformation.

The electrochemical stability of MOFs in aqueous medium is most essential for MOFs based electrocatalysts for hydrogen production via water splitting. Since most MOFs suffer from instability issues in aqueous systems, there is enormous demand for electrochemically stable MOFs catalysts. Herein, we have developed a simple postsynthesis surface modification protocol for La (1,3,5-BTC) (H2O)6 metal-organic frameworks (LaBTC MOFs) using Mercaptopropionic acid (MPA), to attain electrochemical stability in aqueous mediums. The MPA treated LaBTC MOFs exhibited better stability than the bare LaBTC. Further, to facilitate light harvesting properties of LaBTC MOFs, Au nanoparticles (NPs) and CdSe quantum dots (QDs) are functionalized on LaBTC. The sensitization of LaBTC with Au NPs and CdSe QDs enhances the light harvesting properties of LaBTC in the visible region of solar spectrum. Using as a photoanode, the electrode generates the current density of ∼80 mA/cm(2) at 0.8 V (vs Ag/AgCl) during photoelectrochemical water splitting. The heterostructured LaBTC photoanode demonstrates the long-term stability for the period of 10 h. The electrode post-mortem analysis confirms the conversion of CdSe QDs into single crystalline 2D-CdS nanosheets. The present investigation reveals that CdS nanosheets together with SPR Au NPs improve the photoelectrochemical water splitting activity and stability of LaBTC MOFs.