Scalable One-Pot Fabrication of Carbon-Nanofiber-Supported Noble-Metal-Free Nanocrystals for Synergetic-Dependent Green Hydrogen Production: Unraveling Electrolyte and Support Effects.

Electrocatalytic hydrogen evolution reactions (HER) are envisaged as the most promising sustainable approach for green hydrogen production. However, the considerably high cost often associated with such reactions, particularly upon scale-up, poses a daunting challenge. Herein, a facile, effective, and environmentally benign one-pot scalable approach is developed to fabricate MnM (M═Co, Cu, Ni, and Fe) nanocrystals supported over in situ formed carbon nanofibers (MnM/C) as efficient noble-metal-free electrocatalysts for HER. The formation of carbon nanofibers entails impregnating cellulose in an aqueous solution of metal precursors, followed by annealing the mixture at 550 °C. During the impregnation process, cellulose acts as a reactor for inducing the in situ reductions of MnM salts with the assistance of ether and hydroxyl groups to drive the mass production (several grams) of ultralong (5 ± 1 µM) carbon nanofibers ornamented with MnM nanoparticles (10-14 nm in size) at an average loading of 2.87 wt %. For better electrocatalytic HER benchmarking, the fabricated catalysts were tested over different working electrodes, i.e., carbon paper, carbon foam, and glassy carbon, in the presence of different electrolytes. All the fabricated MnM/C catalysts have demonstrated an appealing synergetic-effect-dependent HER activity, with MnCo/C exhibiting the best performance over carbon foam, close to that of the state-of-the-art commercial Pt/C (10 wt % Pt), with an overpotential of 11 mV at 10 mA cm-2, a hydrogen production rate of 2448 mol g-1 h-1, and a prolonged stability of 2 weeks. The HER performance attained by MnCo/C nanofibers is among the highest reported for Pt-free electrocatalysts, thanks to the mutual alloying effect, higher synergism, large surface area, and active interfacial interactions over the nanofibers. The presented findings underline the potential of our approach for the large-scale production of cost-effective electrocatalysts for practical HER.

Interfacial Electronic Interactions within the Pd-CeO2/Carbon Onions Define the Efficient Electrocatalytic Ethanol Oxidation Reaction in Alkaline Electrolytes.

Porous Pd-based electrocatalysts are promising materials for alkaline direct ethanol fuel cells (ADEFCs) and ethanol sensors in the development of renewable energy and point-of-contact ethanol sensor test kits for drunk drivers. However, experimental and theoretical investigations of the interfacial interaction among Pd nanocrystals on supports (i.e., carbon black (CB), onion-like carbon (OLC), and CeO2/OLC) toward ADEFC and ethanol sensors are not yet reported. This is based on the preparation of Pd-CeO2/OLC nanocrystals by the sol-gel and impregnation methods. Evidently, the porous Pd-CeO2/OLC significantly increased membrane-free micro-3D-printed ADEFC performance with a high peak power density (Pmax = 27.15 mW cm-2) that is 1.38- and 7.58-times those of Pd/OLC (19.72 mW cm-2) and Pd/CB (3.59 mW cm-2), besides its excellent stability for 48 h. This is due to the excellent interfacial interaction among Pd, CeO2, and OLC, evidenced by density functional theory (DFT) simulations that showed a modulated Pd d-band center and facile active oxygenated species formation by the CeO2 needed for ethanol fuel cells. Similarly, Pd-CeO2/OLC gives excellent sensitivity (0.00024 mA mM-1) and limit of detection (LoD = 8.7 mM) for ethanol sensing and satisfactory recoveries (89-108%) in commercial alcoholic beverages (i.e., human serum, Amstel beer, and Nederberg Wine). This study shows the excellent possibility of utilizing Pd-CeO2/OLC for future applications in fuel cells and alcohol sensors.

Interfacial Engineering of Porous Pd/M (M = Au, Cu, Mn) Sponge-like Nanocrystals with a Clean Surface for Enhanced Alkaline Electrochemical Oxidation of Ethanol.

The interfacial engineering of Pd-based alloys (i.e., PdM with distinct morphologies, compositions, and strain defects) is an efficient way for enhanced catalytic activity; however, it remains a grand challenge to fabricate such alloys in aqueous solutions without heating, organic solvents, and multiple reaction steps. Herein, we present a simple, aqueous-phase, one-step, and ultrafast approach for the interfacial engineering of surfactant-free porous PdM (M = Cu, Au, and Mn) nanocrystals with well-controlled spongy-like morphology and compositions. The electronic interaction in PdM nanocrystals and their effect on the alkaline electrochemical ethanol oxidation reaction (EOR) are investigated using XRD, XPS, and electrochemical tests. Notably, integrating M metals into Pd atoms results in upshifting the d-band center of Pd and subsequently modulating the EOR activity and stability substantially. The EOR mass activity (10.78 A/mgPd (6.93 A/mgPdCu)) of PdCu was 1.83, 3.09, 4.51, and 53.90 times higher than those of AuPd (5.90 A/mgPd (3.27 A/mgAuPd)), PdMn (3.48 A/mgPd (3.19 A/mgPdMn)), Pd (2.39 A/mgPd), and Pd/C (0.20 A/mgPd), respectively, besides substantial durability after 1000 cycles. This is due to the porous two-dimensional morphology, a low synergetic effect, higher interfacial interaction, and greater active surface area of PdCu, besides a high Cu content with more oxophilicity that facilitates activation/dissociation of H2O to generate -OH species needed for quick EOR electrocatalysis. The electrochemical impedance spectroscopy (EIS) reveals better electrolyte/electrode interfacial interaction and lower charge transfer resistance on PdCu. The EOR activity of PdCu porous sponge-like nanocrystals was superior to all previously reported Pd-based alloys for electrochemical EOR. This study indicates that binary Pd-based catalysts with less synergetic effect are preferred for boosting the EOR activity, which could help in manipulating the surface properties of Pd-based alloys to optimize EOR performance.

A carbon dot-based clay nanocomposite for efficient heavy metal removal.

Carbon dots and their derivatives with fascinating photoluminescence properties have recently attracted tremendous scientific attention. This work describes the preparation of novel fluorescent bentonite clay (B), modified with carbon dot nanomaterials (CDs), and its usage as a lead removal platform. The CDs were prepared using a hydrothermal method from graphitic waste which served as the carbon source material. The as-obtained CDs were found to be fluorescent, being spherical in shape, positively charged, and smaller than 5 nm. Encouraged by their structure and photoluminescence features, they were used as surface modifiers to make fluorescent bentonite nanocomposites. Bentonite was used as a negatively charged model of aluminosilicate and reacted with the positively charged CDs. XRD, FTIR, XPS, and fluorescence analysis were used to characterize the prepared materials. The results indicate that the CDs intercalated inside the bentonite matrix were stable with excellent optical properties over time. They were finally used as an efficient hybrid platform for lead removal with a removal efficiency of 95% under light conditions, at room temperature, in an alkaline medium, and after only 10 min of reaction, compared to 70% under dark conditions. The pseudo-second-order kinetics and Langmuir isotherm models were better fitted to describe the adsorption process. The maximum adsorption capacity was equal to 400 mg g-1 toward Pb(ii) removal, at room temperature and pH = 8, under light conditions. To summarize, we have designed UV light stimuli responsive carbon dot-intercalated clay with high Pb(ii) adsorption capacity and long-term stability.

ZnO-Doped gC3N4 Nanocapsules for Enhancing the Performance of Electroless NiP Coating-Mechanical, Corrosion Protection, and Antibacterial Properties.

A carbon nitride (C3N4) nanomaterial has superior mechanical, thermal, and tribological properties, which make them attractive for various applications, including corrosion-resistant coatings. In this research, newly synthesized C3N4 nanocapsules with different concentrations (0.5, 1.0, and 2.0 wt %) of ZnO as a dopant were incorporated into the NiP coating using an electroless deposition technique. The nanocomposite coatings either ZnO-doped (NiP-C3N4/ZnO) or undoped (NiP-C3N4) were heat-treated at 400 °C for 1 h. The as-plated and heat-treated (HT) nanocomposite coatings were characterized by their morphology, phases, roughness, wettability, hardness, corrosion protection, and antibacterial properties. The results indicated that the microhardness of as-plated and heat-treated nanocomposite coatings was significantly improved after the incorporation of 0.5 wt % ZnO-doped C3N4 nanocapsules. The outcomes of electrochemical studies revealed that the corrosion resistance of the HT coatings is higher than the corresponding as-plated ones. The highest corrosion resistance is achieved on the heat-treated NiP-C3N4/1.0 wt % ZnO coatings. Although the presence of ZnO in the C3N4 nanocapsules increased its surface area and porosity, the C3N4/ZnO nanocapsules prevented localized corrosion by filling the microdefects and pores of the NiP matrix. Furthermore, the colony-counting method used to evaluate the antibacterial behavior of the different coatings demonstrated superior antibacterial properties, namely, after heat treatment. Therefore, the novel perspective C3N4/ZnO nanocapsules can be utilized as a reinforcement nanomaterial in improving the mechanical and anticorrosion performance of NiP coatings in chloride media, together with providing superior antibacterial properties.

Self-Standing Pd-Based Nanostructures for Electrocatalytic CO Oxidation: Do Nanocatalyst Shape and Electrolyte pH Matter?

Tailoring the shape of Pd nanocrystals is one of the main ways to enhance catalytic activity; however, the effect of shapes and electrolyte pH on carbon monoxide oxidation (COOxid) is not highlighted enough. This article presents the controlled fabrication of Pd nanocrystals in different morphologies, including Pd nanosponge via the ice-cooling reduction of the Pd precursor using NaBH4 solution and Pd nanocube via ascorbic acid reduction at 25 °C. Both Pd nanosponge and Pd nanocube are self-standing and have a high surface area, uniform distribution, and clean surface. The electrocatalytic CO oxidation activity and durability of the Pd nanocube were significantly superior to those of Pd nanosponge and commercial Pd/C in only acidic (H2SO4) medium and the best among the three media, due to the multiple adsorption active sites, uniform distribution, and high surface area of the nanocube structure. However, Pd nanosponge had enhanced COOxid activity and stability in both alkaline (KOH) and neutral (NaHCO3) electrolytes than Pd nanocube and Pd/C, attributable to its low Pd-Pd interatomic distance and cleaner surface. The self-standing Pd nanosponge and Pd nanocube were more active than Pd/C in all electrolytes. Mainly, the COOxid current density of Pd nanocube in H2SO4 (5.92 mA/cm2) was nearly 3.6 times that in KOH (1.63 mA/cm2) and 10.3 times that in NaHCO3 (0.578 mA/cm2), owing to the greater charge mobility and better electrolyte-electrode interaction, as evidenced by electrochemical impedance spectroscopy (EIS) analysis. Notably, this study confirmed that acidic electrolytes and Pd nanocube are highly preferred for promoting COOxid and may open new avenues for precluding CO poisoning in alcohol-based fuel cells.

Unveiling the effect of shapes and electrolytes on the electrocatalytic ethanol oxidation activity of self-standing Pd nanostructures.

Morphologically controlled Pd-based nanocrystals are the most efficient strategies for improving the electrocatalytic ethanol oxidation reaction (EOR) performance; however, their morphological-EOR activity relationship and effect of electrolytes at a wide pH range are still ambiguous. Here, we have synthesized porous self-standing Pd clustered nanospheres (Pd-CNSs) and Pd nanocubes (Pd-NCBs) for the EOR in acidic (H2SO4), alkaline (KOH), and neutral (NaHCO3) electrolytes compared to commercial spherical-like Pd/C catalysts. The fabrication process comprises the ice-cooling reduction of Pd precursor by sodium borohydride (NaBH4) and l-ascorbic acid to form Pd-CNSs and Pd-NCBs, respectively. The EOR activity of Pd-CNSs significantly outperformed those of Pd-NCBs, and Pd/C in all electrolytes, but the EOR activity was better in KOH than in H2SO4 and NaHCO3. This is due to the 3D porous clustered nanospherical morphology that makes Pd active centers more accessible and maximizes their utilization during EOR. The EOR specific/mass activities of Pd-CNSs reached (8.51 mA/cm2/2.39 A/mgPd) in KOH, (2.98 mA/cm2/0.88 A/mgPd) in H2SO4, and (0.061 mA/cm2/0.0083 A/mgPd) in NaHCO3, in addition to stability after 1000 cycles. This study affirms that porous 3D spherical Pd nanostructures are preferred for the EOR than those of 0D spherical-like and multi-dimensional cube-like nanostructures.

Template free synthesis of CuO nanocomposite for catalytic hydrogenation of CO2.

Increasing CO2 emissions from industry has disastrous consequences for the environment. Effective utilization of CO2 as a carbon source can address the environmental challenges, and we can address the energy crisis caused by fossil fuel consumption. Electrochemical conversion of CO2 is a promising method recently gaining widespread popularity. Its high productivity, however, remains a major challenge. This work involved a facile novel preparation of a suitable CuO nanocomposite to reduce CO2 into useful fuels effectively. Hydrothermal synthesis was used to synthesize the nanocomposite. The synthesized NC's structure, morphology, and elemental analysis were evaluated using XRD, Raman spectroscopy, SEM, and TEM. ICP-OES analysis was performed to quantify Cu concentration in the CuO composite, confirming 98.6% of Cu of the prepared matrix. The cyclic voltammetry method has been used to study the electrochemical activity of NC for CO2 reduction. Additionally, the NMR & GC-MS analyses were performed to identify the product. Regarding CO2 reduction, the NC performed greatly better than the ordinary CuO. In addition, the NC exhibits high structural stability and durability, demonstrating its potential to reduce CO2 into fuels.

Evaluation of the Influence of Eggshell (ES) Concentration on the Degradation Behavior of Mg-2.5Zn Biodegradable Alloy in Simulated Body Fluid.

Currently, permanent vascular stents are fabricated using titanium and stainless steel implants that are nondegradable and offer high stability, but they have certain disadvantages. For example, the prolonged exposition of aggressive ions in the physiological media and the existence of defects in the oxide film create conditions for corrosion to occur, thus triggering unwanted biological events and compromising the mechanical integrity of the implants. Moreover, when the implant does not need to be permanent, there is the need to submit the patient for a second surgery for implant removal. As a solution for nonpermanent implants, biodegradable magnesium alloys have been deemed a promising substitute, for example, for cardiovascular-related applications and the construction of orthopedic devices. A biodegradable magnesium alloy (Mg-2.5Zn) reinforced by zinc and eggshell was employed in this study as an environment-conscious magnesium (eco) composite (Mg-2.5Zn-xES). Disintegrated melt deposition (DMD) was used to fabricate the composite. Experimental studies were conducted to investigate the biodegradation performance of Mg-Zn alloys containing 3 and 7 wt % eggshell (ES) in simulated body fluid (SBF) at 37 °C. Different corrosion techniques were used to study the corrosion behavior of the Mg-2.5Zn-xES composites, including weight loss measurements, hydrogen evolution, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and scanning vibrating electrode technique (SVET). Scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) were employed to scrutinize the corroded surfaces' morphology and composition. The outcomes indicated that Mg-2.5Zn-3ES possesses the lowest degradation activity.

Pt-Based Nanostructures for Electrochemical Oxidation of CO: Unveiling the Effect of Shapes and Electrolytes.

Direct alcohol fuel cells are deemed as green and sustainable energy resources; however, CO-poisoning of Pt-based catalysts is a critical barrier to their commercialization. Thus, investigation of the electrochemical CO oxidation activity (COOxid) of Pt-based catalyst over pH ranges as a function of Pt-shape is necessary and is not yet reported. Herein, porous Pt nanodendrites (Pt NDs) were synthesized via the ultrasonic irradiation method, and its CO oxidation performance was benchmarked in different electrolytes relative to 1-D Pt chains nanostructure (Pt NCs) and commercial Pt/C catalyst under the same condition. This is a trial to confirm the effect of the size and shape of Pt as well as the pH of electrolytes on the COOxid. The COOxid activity and durability of Pt NDs are substantially superior to Pt NCs and Pt/C in HClO4, KOH, and NaHCO3 electrolytes, respectively, owing to the porous branched structure with a high surface area, which maximizes Pt utilization. Notably, the COOxid performance of Pt NPs in HClO4 is higher than that in NaHCO3, and KOH under the same reaction conditions. This study may open the way for understanding the COOxid activities of Pt-based catalysts and avoiding CO-poisoning in fuel cells.

Pd/Ni-metal-organic framework-derived porous carbon nanosheets for efficient CO oxidation over a wide pH range.

Metal nanocrystal ornamented metal-organic frameworks (MOFs) are of particular interest in multidisciplinary applications; however, their electrocatalytic CO oxidation performance over wide pH ranges is not yet reported. Herein, Ni-MOF-derived hierarchical porous carbon nanosheets (Ni-MOF/PC) with abundant Ni-N x sites decorated with Pd nanocrystals (Pd/Ni-MOF/PC) were synthesized by microwave-irradiation (MW-I) followed by annealing at 900 °C and subsequent etching of Ni-MOF/C prior to Pd deposition. The fabrication mechanism comprises the generation of self-reduced reducing gases from triethylamine during the annealing and selective chemical etching of Ni, thereby facilitating the reduction of Ni-anchored MOF and Pd nanocrystal deposition with the aid of ethylene glycol and MW-I to yield Pd/Ni-N x enriched MOF/PC. The synthetic strategies endear the Pd/Ni-MOF/PC with unique physicochemical merits: abundant defects, interconnected pores, high electrical conductivity, high surface area, Ni-deficient but more active sites for Pd/Ni-N x in porous carbon nanosheets, and synergism. These merits endowed the CO oxidation activity and stability on Pd/Ni-MOF/PC substantially than those of Pd/Ni-MOF/C and Pd/C catalysts in wide pH conditions (i.e., KOH, HClO4, and NaHCO3). The CO oxidation activity study reveals the utilization of MOF/PC with metal nanocrystals (Pd/Ni) in CO oxidation catalysis.

A realistic perspective for CO2 triggered tuning of electrical conductivity.

To seek sustainable CO2 sequestration and conversion, an electrochemical cell has been investigated for carbon capture and utilization strategy (CCU). In this cell, atmospheric CO2 is captured under ambient conditions and incorporated into power generation using zinc nanopowder as the catalyst. As a result, a method was developed to tune the electronic property of zinc by passing CO2. It was observed that nearly three orders of magnitude of conductivity could be changed along with achieving a carbon capture strategy. The system also exhibited good stability. In this process, it was observed that efficient current generation could be achieved due to zinc's active participation as a catalyst. The detailed physicochemical characterizations of catalysts were also examined. XRD, FTIR and TEM analysis perform the structural and morphological characterization. The system performance was further investigated using different criteria.

Vapour-Phase Selective Hydrogenation of γ-Valerolactone to 2-Methyltetrahydrofuran Biofuel over Silica-Supported Copper Catalysts.

2-Methyltetrahydrofuran (MTHF) is a desirable biomass-based platform chemical with excellent potential as an ideal biofuel, green solvent, and raw material for synthesizing downstream chemicals. In this work, a series of copper nanoparticles encapsulated on SiO2 were prepared by the wet impregnation method and evaluated as efficient non-noble metal catalysts for the vapour-phase hydrogenation of γ-valerolactone (GVL) to MTHF in a fixed-bed reactor under mild reaction conditions. The obtained catalyst properties were determined by XRD, FE-SEM, TEM, UV-DRS, TPR, NH3-TPD, N2O decomposition and pore size distribution measurements. Meanwhile, the parameters/variables tuning their catalytic performance (activity, conversion, selectivity and stability) were examined. Various Cu loadings featured on the SiO2 support are essential for tuning the catalytic activity. Among the catalysts tested, a 5 wt% Cu/SiO2 catalyst showed a 97.2% MTHF selectivity with 71.9% GVL conversion, and showed a stability for 33 h time-on-stream, achieved at 260 °C and atmospheric pressure conditions. It was found that a huge dispersion of Cu metal in support, hydrogen activation ability, abundant acidic sites and surface area are all beneficial for improved MTHF selectivity.

An Eco-Friendly Quaternary Ammonium Salt as a Corrosion Inhibitor for Carbon Steel in 5 M HCl Solution: Theoretical and Experimental Investigation.

The corrosion of industrial material is a costly problem associated with global economic losses reaching trillions of US dollars in the repair of failures. Injecting corrosion inhibitors is the most practically promising method for decelerating corrosion reactions and protecting surfaces. Recent investigations have focused on surfactants as corrosion inhibitors due to their amphiphilic nature, low cost, and simple chemical preparation procedures. This study aims to investigate the performance of an environment-friendly Quaternium-22 (Q-22) surfactant which is widely used in cosmetics for C-steel corrosion inhibition in a 5 M HCl medium. Weight loss experiments were performed at different concentrations and immersion times, presenting a maximum efficiency at 2.22 mmol·L-1. The influence of Q-22 on the corrosion behavior of C-steel was elucidated using non-destructive electrochemical measurements. The overall results revealed that adding varied concentrations of Q-22 significantly decreases the corrosion rate of C-steel. The results revealed the physisorption nature of Q-22 onto the C-steel surface, with adsorption following the Freundlich isotherm (∆Hads= -16.40 kJ·mol-1). The relative inhibition performance of Q-22 was also evaluated by SEM and AFM analyses. Lastly, quantum chemical calculations based on density functional theory (DFT) demonstrated that Q-22 has promising molecular features concerning the anticorrosive mechanism.

Pd-Nanoparticles Embedded Metal-Organic Framework-Derived Hierarchical Porous Carbon Nanosheets as Efficient Electrocatalysts for Carbon Monoxide Oxidation in Different Electrolytes.

Rational synthesis of Co-ZIF-67 metal-organic framework (MOF)-derived carbon-supported metal nanoparticles is essential for various energy and environmental applications; however, their catalytic activity toward carbon monoxide (CO) oxidation in various electrolytes is not yet emphasized. Co-ZIF-67-derived hierarchical porous carbon nanosheet-supported Pd nanocrystals (Pd/ZIF-67/C) were prepared using a simple microwave-irradiation approach followed by carbonization and etching. Mechanistically, during microwave irradiation, triethyleneamine provides abundant reducing gases that promote the formation of Pd nanoparticles/Co-Nx in porous carbon nanosheets with the assistance of ethylene glycol and also form a multimodal pore size. The electrocatalytic CO oxidation activity and stability of Pd/ZIF-67/C outperformed those of commercial Pd/C and Pt/C catalysts by (4.2 and 4.4, 4.0 and 2.7, 3.59 and 2.7) times in 0.1 M HClO4, 0.1 M KOH, and 0.1 M NaHCO3, respectively, due to the catalytic properties of Pd besides the conductivity of Co-Nx active sites and delicate porous structures of ZIF-67. Notably, using Pd/ZIF-67/C results in a higher CO oxidation activity than Pd/C and Pt/C. This study may pave the way for using MOF-supported multi-metallic nanoparticles for CO oxidation electrocatalysis.

Hierarchical Porous Carbon Nitride-Crumpled Nanosheet-Embedded Copper Single Atoms: An Efficient Catalyst for Carbon Monoxide Oxidation.

Rational design of metal single-site embedded porous graphitic carbon nitride (P-g-C3N4) nanostructures exploiting maximum atom utilization is warranted to enhance the thermal CO oxidation (COOx) reaction. Herein, a facile, green, one-pot, and template-free approach is developed to fabricate the hierarchical porous P-g-C3N4-crumpled ultrathin nanosheets atomically doped with copper single atoms (Cu-P-g-C3N4). Mechanistically, the quick protonation of melamine and pyridine under acidic conditions induces deamination to form melem, which is polycondensed under heating. The interconnected pores, high surface area (240 m2g-1), and maximized exposed isolated Cu atomic active sites (1.8 wt %) coordinated with nitrogen atom P-g-C3N4 are the salient features of Cu- P-g-C3N4 that endowed complete conversion to CO2 at 184 °C. In contrast, P-g-C3N4 only converted 3.8% of CO even at 350 °C, implying the electronic effect of Cu single atoms. The abundant Cu-nitrogen moieties can drastically weaken the binding affinity of the CO-oxidation (COOx) intermediates and products, thus accelerating the reaction kinetics at a low temperature. This study may promote the fabrication of P-g-C3N4 doped with various single atoms for the oxidation of CO.

Low Platinum-Loaded Molybdenum Co-catalyst for the Hydrogen Evolution Reaction in Alkaline and Acidic Media.

Developing an efficient catalytic system for electrolysis with reduced platinum (Pt) loading while maintaining performance comparable to bulk platinum metal is important to decrease costs and improve scalability of the hydrogen fuel economy. Here we report the performance of a novel sputter-deposited molybdenum (Mo) thin film with an extremely low co-loading of Pt, where Pt atoms were dispersed on Mo (Ptd-Mo) as an electrocatalyst for the hydrogen evolution reaction (HER) in either alkaline or acidic media. The Ptd-Mo electrocatalyst presents similar catalytic activity to bulk Pt in alkaline media, while the performance is only slightly decreased in acidic media. Differential electrochemical mass spectrometry (DEMS) results confirm that the Ptd-Mo electrocatalyst produced hydrogen at a rate comparable with that of a pristine Pt sample at the same potential. A comparison with Pt-loaded degenerately doped p-type doped silicon (Ptd-Si) suggests that Mo and Pt work synergistically to boost the performance of Ptd-Mo catalysts. Cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) before and after 1000 cycles of continuous operation confirm the significant durability of the Ptd-Mo performance. Overall, the Ptd-Mo electrocatalyst, with comparable HER activity to bulk Pt despite an ultra-low Pt loading, could be a strong candidate for hydrogen production in either acidic or basic conditions.

Porous spinel-type transition metal oxide nanostructures as emergent electrocatalysts for oxygen reduction reactions.

Porous spinel-type transition metal oxide (PS-TMO) nanocatalysts comprising two kinds of metal (denoted as AxB3-xO4, where A, B = Co, Ni, Zn, Mn, Fe, V, Sm, Li, and Zn) have emerged as promising electrocatalysts for oxygen reduction reactions (ORRs) in energy conversion and storage systems (ECSS). This is due to the unique catalytic merits of PS-TMOs (such as p-type conductivity, optical transparency, semiconductivity, multiple valence states of their oxides, and rich active sites) and porous morphologies with great surface area, low density, abundant transportation paths for intermediate species, maximized atom utilization and quick charge mobility. In addition, PS-TMOs nanocatalysts are easily prepared in high yield from Earth-abundant and inexpensive metal precursors that meet sustainability requirements and practical applications. Owing to the continued developments in the rational synthesis of PS-TMOs nanocatalysts for ORRs, it is utterly imperative to provide timely updates and highlight new advances in this research area. This review emphasizes recent research advances in engineering the morphologies and compositions of PS-TMOs nanocatalysts in addition to their mechanisms, to decipher their structure-activity relationships. Also, the ORR mechanisms and fundamentals are discussed, along with the current barriers and future outlook for developing the next generation of PS-TMOs nanocatalysts for large-scale ECSS.

Cu and Ni Co-sputtered heteroatomic thin film for enhanced nonenzymatic glucose detection.

In this work, we report a wafer-scale and chemical-free fabrication of nickel (Ni) and copper (Cu) heteroatomic Cu-Ni thin films using RF magnetron sputtering technique for non-enzymatic glucose sensing application. The as-prepared wafer-scale Cu-Ni thin films exhibits excellent electrocatalytic activity toward glucose oxidation with a 1.86 µM detection limit in the range of 0.01 mM to 20 mM range. The Cu-Ni film shows 1.3- and 5.4-times higher glucose oxidation activity in comparison to the Cu and Ni electrodes, respectively. The improved electrocatalytic activity is attributed to the synergistic effect of the bimetallic catalyst and high density of grain boundaries. The Cu-Ni electrodes also possessed excellent anti-interference characteristics. These results indicate that Cu-Ni heteroatomic thin film can be a potential candidate for the development of non-enzymatic glucose biosensor because of its chemical free synthesis, excellent reproducibility, reusability, and long-term stability.

A Smart Colorimetric Platform for Detection of Methanol, Ethanol and Formic Acid.

Carbon dioxide (CO2) is a greenhouse gas in the atmosphere and scientists are working on converting it to useful products, thereby reducing its quantity in the atmosphere. For converting CO2, different approaches are used, and among them, electrochemistry is found to be the most common and more efficient technique. Current methods for detecting the products of electrochemical CO2 conversion are time-consuming and complex. To combat this, a simple, cost-effective colorimetric method has been developed to detect methanol, ethanol, and formic acid, which are formed electrochemically from CO2. In the present work, the highly efficient sensitive dyes were successfully established to detect these three compounds under optimized conditions. These dyes demonstrated excellent selectivity and showed no cross-reaction with other products generated in the CO2 conversion system. In the analysis using these three compounds, this strategy shows good specificity and limit of detection (LOD, ~0.03-0.06 ppm). A cost-effective and sensitive Internet of Things (IoT) colorimetric sensor prototype was developed to implement these dyes systems for practical and real-time application. Employing the dyes as sensing elements, the prototype exhibits unique red, green, and blue (RGB) values upon exposure to test solutions with a short response time of 2 s. Detection of these compounds via this new approach has been proven effective by comparing them with nuclear magnetic resonance (NMR). This novel approach can replace heavy-duty instruments such as high-pressure liquid chromatography (HPLC), gas chromatography (G.C.), and NMR due to its extraordinary selectivity and rapidity.