Platinum (Pt)-based-nanomaterials are currently the most successful catalysts for the oxygen reduction reaction (ORR) in electrochemical energy conversion devices such as fuel cells and metal-air batteries. Nonetheless, Pt catalysts have serious drawbacks, including low abundance in nature, sluggish kinetics, and very high costs, which limit their practical applications. Herein, we report the first rationally designed nonprecious Co–Cu bimetallic metal–organic framework (MOF) using a low-temperature hydrothermal method that outperforms the electrocatalytic activity of Pt/C for ORR in alkaline environments. The MOF catalyst surpassed the ORR performance of Pt/C, exhibiting an onset potential of 1.06 V vs RHE, a half-wave potential of 0.95 V vs RHE, and a higher electrochemical stability (ΔE 1/2 = 30 mV) after 1000 ORR cycles in 0.1 M NaOH. Additionally, it outperformed Pt/C in terms of power density and cyclability in zinc-air batteries. This outstanding behavior was attributed to the unique electronic synergy of the Co−Cu bimetallic centers in the MOF network, which was revealed by XPS and PDOS.
The design of alternative earth-abundant van der Waals (vdW) nanoheterostructures for bifunctional oxygen evolution/reduction (OER/ORR) electrocatalysis is of paramount importance to fabricate energy-related devices. Herein, we report a simple metal−organic framework (MOF)-derived synthetic strategy to fabricate low-dimensional (LD) nanohybrids formed by zerodimensional (0D) ZrO 2 nanoparticles (NPs) and heteroatomdoped two-dimensional (2D) carbon nanostructures. The 2D platforms controlled the electronic structures of interfacial Zr atoms, thus producing optimized electron polarization for boron and nitrogen-doped carbon (BCN)/ZrO 2 nanohybrids. X-ray photoelectron spectroscopy (XPS) and theoretical studies revealed the key role of the synergistic couple effect of boron (B) and nitrogen (N) in interfacial electronic polarization. The BCN/ZrO 2 nanohybrid showed excellent bifunctional electrocatalytic activity, delivering an overpotential (η 10 ) of 301 mV to reach a current density of 10 mA−cm −2 for the OER process and a half-wave potential (E 1/2 ) of 0.85 V vs reversible hydrogen electrode (RHE) for the ORR process, which are comparable to the state-of-the-art LD nanohybrids. Furthermore, BCN/ZrO 2 also showed competitive performances for water-splitting and zinc−air battery devices. This work establishes a new route to fabricate highly efficient multifunctional electrocatalysts by tuning the electronic polarization properties of 0D−2D electrochemical interfaces.
Facile electron transport and intimate electronic contact at the catalyst–electrode interface are critical for the ideal performance of electrochemical devices such as glucose biofuel cells and biosensors. Here, through a comprehensive experimental–theoretical exploration, we demonstrate that engineering of interfacial properties, including interfacial electron dynamics, electron affinity, electrode–catalyst–adsorbate electrical synergy, and electrocatalytically active surface area, can lead to highly efficient graphene-based electrochemical devices. We selected two closely related but electronically and surface chemically different functionalized graphene analoguesgraphene acid (GA) and reduced graphene oxide (rGO)as the model graphenic platforms. Our studies reveal that compared to rGO, GA is a superior bifunctional catalyst with high oxygen reduction reaction (an onset potential of 0.8 V) and good glucose oxidation activities. Spectroscopic and electrochemical analysis of GA and rGO indicated that the higher carboxylic acid content on GA increases its overall electron affinity and coupled with improved conductivity and band alignment, which leads to GA’s better electrochemical performance. The formulation of a heterostructure between GA and samarium oxide (Sm2O3) nanoparticles led to augmented conductivity (lower charge-transfer resistance) and glucose binding affinity, resulting in a further enhanced glucose oxidation activity. The interdimensional Sm2O3/GA heterostructure, leveraging their enhanced glucose oxidation capacity, exhibited excellent nonenzymatic amperometric glucose sensing performance, with a detection limit of 107 nM and a sensitivity of 20.8 μA/μM. Further, a nonenzymatic, membrane-free glucose biofuel cell (with Sm2O3/GA heterostructure as anode and GA as biocathode) produced a power density of 3.2 μW·cm–2 (in PBS spiked with 3 mM glucose), which can function as self-powered glucose sensors with 70 nM limit of detection. The study establishes the potential of interfacial engineering of GA to engage it as a highly tunable substrate for a broad range of electrochemical applications, especially in future self-powered biosensors.
The thermoelectric effect encompasses three different effects, i.e. Seebeck effect, Peltier effect, and Thomson effect, which are considered as thermally activated materials that alter directions in smart materials. It is currently considered one of the most challenging green energy harvesting mechanisms among researchers. The ability to utilize waste thermal energy that is generated by different applications promotes the use of thermoelectric harvesters across a wide range of applications. This review illustrates the different attempts to fabricate efficient, robust and sustainable thermoelectric harvesters, considering the material selection, characterization, device fabrication and potential applications. Thermoelectric harvesters with a wide range of output power generated reaching the milliwatt range have been considered in this work, with a special focus on the main advantages and disadvantages in these devices. Additionally, this review presents various studies reported in the literature on the design and fabrication of thermoelectric harvesters and highlights their potential applications. In order to increase the efficiency of equipment and processes, the generation of thermoelectricity via thermoelectric materials is achieved through the harvesting of residual energy. The review discusses the main challenges in the fabrication process associated with thermoelectric harvester implementation, as well as the considerable advantages of the proposed devices. The use of thermoelectric harvesters in a wide range of applications where waste thermal energy is used and the impact of the thermoelectric harvesters is also highlighted in this review.
Graphene–gold nanocomposite materials combined with (5-fluorouracil, 5-FU) drug show high potent cytotoxicity against MCF-7 cells, can decrease HER-2 gene expression and cause cell cycle arrest.
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