NixCo1-x@NixCo1-xO/NCNT as Trifunctional ORR, OER, and HER Electrocatalysts and its Application in a Zn-Air Battery.

The efficient electrochemical conversion and storage devices can be boosted by the development of cost-effective and durable electrocatalysts. However, simultaneous in-depth understanding of the reaction mechanism is also required. Herein, we report the preparation, characterization, and electrochemical activities of bimetallic NixCo1-x NPs and core-shell NixCo1-x@NixCo1-xO NPs stabilized on N-doped carbon nanotubes (NCNTs). The electrocatalyst is derived from a bimetallic MOF {[Ni0.5Co0.5(bpe)2(N(CN)2)](N(CN)2)·(5H2O)}n (1) via pyrolysis followed by calcination. Pyrolysis of the bimetallic MOF gives rise to bimetallic nanoparticles stabilized on NCNTs, which, when subsequently calcined, leads to the formation of a core-shell structure with a semiconducting oxide shell (NixCo1-xO) encapsulating the NixCo1-x bimetallic NP core. Detailed evaluation of the electrocatalytic performance of NixCo1-x@NixCo1-xO/NCNT proves its worth as a bifunctional catalyst with 380 mV overpotential for oxygen evolution reaction at 10 mA cm-2 current density and 0.87 V (vs RHE) onset for oxygen reduction reaction in the alkaline medium. Additionally, the prepared electrocatalyst efficiently catalyzes the hydrogen evolution reaction with a nominal overpotential of 74 mV (vs RHE) for reaching 10 mA cm-2 current density in acidic medium. The practical applicability of this catalyst is further upheld in the fabrication of a zinc-air battery having high specific capacity with high round-trip efficiency and adequate cycle life. DFT calculations establish that the structure of NixCo1-x@NixCo1-xO/NCNT is crucial for its electrochemical activity since it has the threefold advantages of cooperative charge transfer from Co to Ni, synergistic relationship between the conductive alloy core and semiconducting oxide shell, and a highly conductive N-doped CNT matrix.

Inverse 'intra-lattice' charge transfer in nickel-molybdenum dual electrocatalysts regulated by under-coordinating the molybdenum center.

The prevalence of intermetallic charge transfer is a marvel for fine-tuning the electronic structure of active centers in electrocatalysts. Although Pauling electronegativity is the primary deciding factor for the direction of charge transfer, we report an unorthodox intra-lattice 'inverse' charge transfer from Mo to Ni in two systems, Ni73Mo alloy electrodeposited on Cu nanowires and NiMo-hydroxide (Ni : Mo = 5 : 1) on Ni foam. The inverse charge transfer deciphered by X-ray absorption fine structure studies and X-ray photoelectron spectroscopy has been understood by the Bader charge and projected density of state analyses. The undercoordinated Mo-center pushes the Mo 4d-orbitals close to the Fermi energy in the valence band region while Ni 3d-orbitals lie in the conduction band. Since electrons are donated from the electron-rich Mo-center to the electron-poor Ni-center, the inverse charge transfer effect navigates the Mo-center to become positively charged and vice versa. The reverse charge distribution in Ni73Mo accelerates the electrochemical hydrogen evolution reaction in alkaline and acidic media with 0.35 and 0.07 s-1 turnover frequency at -33 ± 10 and -54 ± 8 mV versus the reversible hydrogen electrode, respectively. The corresponding mass activities are 10.5 ± 2 and 2.9 ± 0.3 A g-1 at 100, and 54 mV overpotential, respectively. Anodic potential oxidizes the Ni-center of NiMo-hydroxide for alkaline water oxidation with 0.43 O2 s-1 turnover frequency at 290 mV overpotential. This extremely durable homologous couple achieves water and urea splitting with cell voltages of 1.48 ± 0.02 and 1.32 ± 0.02 V, respectively, at 10 mA cm-2.

Microbial originated surfactants with multiple applications: a comprehensive review.

Microbial synthesized surfactants are used in contaminated soil bioremediation processes and have multiple applications in various industries. These compounds minimize the negative influences in soil via absorption by detoxifying the toxic metals or compounds. Further, applications of biosurfactants are detected in treating chronic diseases or synthetic drugs alternatives in current periods. Various surfactant molecules can provide many benefits due to their diversities in structural and functional groups. These compounds showed a wide array of applications in multiple sectors such as biomedical or pharmaceutical fields. Agricultural, food processing, laundry, or other sectors. Many microbial systems or plant cells are utilized in biosurfactant production as confirmed by biochemical analysis of genome sequencing tools. Biosurfactant compounds can alter drug transport across the cell membrane. Different nature of biosurfactant compounds exhibited their antifungal, antibacterial, antiviral activities, or antiadhesive coating agents used in reduction of many hospital infections. These distinct properties of biosurfactants pushed their broad spectrum applications in biomedical, agriculture sectors and bioremediation tasks. Additionally, many strains of fungi or bacteria are utilized for biosurfactant synthesis involved in the detoxification of soil/other components of the environment. In these reviews, authors explained various biosurfactants molecules and their mode of actions. Also, applications of microbial originated biosurfactants along with their process technologies are described. Future perspectives of biosurfactants and their scope are also critically explained so that this review paper can be used as a showcase for production and application of biosurfactants.

Potassium Cobalt Pyrophosphate as a Nonprecious Bifunctional Electrocatalyst for Zinc-Air Batteries.

Economic and sustainable (ecological) energy storage forms a major pillar of the global energy sector. Bifunctional electrocatalysts, based on oxygen electrolysis, play a key role in the development of rechargeable metal-air batteries. Pursuing precious metal-free economic catalysts, here, we report K2CoP2O7 pyrophosphate as a robust cathode for secondary zinc-air batteries with efficient oxygen evolution and oxygen reduction (OER||ORR) activity. Prepared by autocombustion, nanoscale K2CoP2O7 exhibited excellent oxygen reduction and evolution reactions among all phosphate-based electrocatalysts. In particular, the OER activity surpassed that of commercial RuO2 with low overpotential (0.27 V). First-principles calculations revealed that the bifunctional activity is rooted in the Co active site with the CoO5 local coordination in the most stable (110) surface. This nanostructured (tetragonal) pyrophosphate can be harnessed as an economic bifunctional catalyst for zinc-air batteries.

Explaining the Advantageous Impact of Tertiary versus Secondary Nitrogen Center on the Activity of PNP-Pincer Co(I)-Complexes for Catalytic Hydrogenation of CO2.

Pincer ligated coordination complexes of base metals have shown remarkable catalytic activity for hydrogenation/dehydrogenation of CO2 . The recently reported MeN[CH2 CH2 (i Pr2 )]2 Co(I)PNP-pincer complex was shown to exhibit substantially higher catalytic activity in comparison to the corresponding catalyst, HN[CH2 CH2 (i Pr2 )]2 Co(I)PNP, bearing a secondary nitrogen center on the pincer ligand. Here, we computationally investigate the mechanisms for hydrogenation of CO2 to formate catalyzed by these two Co-PNP complexes to explain how such a small structural difference could have a sizable impact on their catalytic activity. Plausible hydrogenation routes were examined in details and our findings provide solid support for the experimental observations. Our results reveal that such trends in catalytic activity could be explained from the lower activation barrier for the hydride transfer step upon changing the pincer nitrogen center from secondary to tertiary.

MOF Derived Co3O4@Co/NCNT Nanocomposite for Electrochemical Hydrogen Evolution, Flexible Zinc-Air Batteries, and Overall Water Splitting.

Toward the goal of clean and sustainable energy source, the development of a trifunctional electrocatalyst is a boon for energy storage and conversion devices such as regenerative fuel cells and metal-air batteries. MOF-derived semiconducting-metallic core-shell electrocatalyst Co3O4@Co/NCNT (NCNT = nitrogen-doped carbon nanotube), which was shown to catalyze oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), is also found to be an active electrocatalyst for hydrogen evolution reaction (HER) with a low overpotential of 171 mV. Here, the HER activity of Co3O4@Co/NCNT is presented and is shown as highly efficient and robust trifunctional electrocatalyst. The detailed theoretical calculation has found N-center of Co-N4 moiety to be the H+ binding active site and thus proves Co3O4@Co/NCNT to be active for HER. Further, the ORR and OER bifunctionality of Co3O4@Co/NCNT helped in fabricating secondary Zn-air battery with high power density of 135 mW/cm2. Also, an all-solid-state flexible and wearable battery with Co3O4@Co/NCNT as cathode and electrodeposited Zn on carbon fiber cloth as anode was shown to withstand its performance even under stressed conditions. Finally, the material being trifunctional in nature was used both as an anode and cathode material for the electrolysis of water, which was powered by the Zn-air batteries with Co3O4@Co/NCNT as the cathode material. It is believed that the development of a trifunctional catalyst would help in wide commercialization of regenerative fuel cells.