Interfacial Carbon Makes Nano-Particulate RuO2 an Efficient, Stable, pH-Universal Catalyst for Splitting of Seawater.

An electrocatalyst composed of RuO2 surrounded by interfacial carbon, is synthesized through controllable oxidization-calcination. This electrocatalyst provides efficient charge transfer, numerous active sites, and promising activity for pH-universal electrocatalytic overall seawater splitting. An electrolyzer with this catalyst gives current densities of 10 mA cm-2 at a record low cell voltage of 1.52 V, and shows excellent durability at current densities of 10 mA cm-2 for up to 100 h. Based on the results, a mechanism for the catalytic activity of the composite is proposed. Finally, a solar-driven system is assembled and used for overall seawater splitting, showing 95% Faraday efficiency.

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.

Hierarchically Fractal PtPdCu Sponges and their Directed Mass- and Electron-Transfer Effects.

Fractal Pt-based materials with hierarchical structures and high self-similarity have attracted more and more attention due to their bioinspiring maximum optimization of energy utilization and mass transfer. However, their high-efficiency design of the mass- and electron-transfer still remains to be a great challenge. Herein, fractal PtPdCu hollow sponges (denoted as PtPdCu-HS) facilitating both directed mass- and electron-transfer are presented. Such directed transfer effects greatly promote electrocatalytic activity, regarded as 3.9 times the mass activity, 7.3 times the specific activity, higher poison tolerance, and higher stability than commercial Pt/C for the methanol oxidation reaction (MOR). A new "directed mass- and electron-transfer" concept, characteristics, and mechanism are proposed at the micro/nanoscale to clarify the structural design and functional enhancement of fractal electrocatalyst. This work displays new possibilities for designing novel nanomaterials with high activity and superior stability toward electrocatalysis or other practical applications.

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.

Ultimate Corrosion to Pt-Cu Electrocatalysts for Enhancing Methanol Oxidation Activity and Stability in Acidic Media.

Alloying platinum (Pt) with transition metals (M), as an established class of electrocatalysts, reduces the use of Pt and improves the electrocatalytic performance. However, the stability of transition metals in nanostructured platinum alloys is a fundamental and practical problem in electrocatalysis, due to leaching of transition metals under acidic operating condition. Here, a corrosion method has been developed for a Pt-Cu electrocatalyst with high activity (6.6 times that of commercial Pt/C) and excellent stability for the methanol oxidation reaction (MOR) under acidic operating conditions. The mechanism of formation has been studied, and possible mesostructured re-formation and atomic re-organization have been proposed. This work offers an effective strategy for the facile synthesis of a highly acid-stable PtM alloying and opens a door to high-performance design for electrocatalysts.

Titanium Vacancies in TiO2 Nanofibers Enable Highly Efficient Photodriven Seawater Splitting.

Photodriven seawater splitting is considered to be one of the most promising techniques for sustainable hydrogen production. However, the high salinity of seawater would deactivate catalysts and consume the photogenerated carriers. Metal vacancies in metal oxide semiconductors are critical to directed electron transfer and high salinity resistance; they are thus desirable but remain a challenge. We demonstrate a facile controllable calcination approach to synthesize TiO2 nanofibers with rich Ti vacancies with excellent photo/electro performances and long-time stability in photodriven seawater splitting, including photocatalysis and photo-electrocatalysis. Experimental measurements and theoretical calculations reveal the formation of titanium vacancies, as well as unidirectional electron trap and superior H+ adsorption ability for efficient charge transfer and resistance to corrosion by seawater. Therefore, atomic-/nanoscale characteristics and mechanism have been proposed to clarify the generation of titanium vacancies and the corresponding interfacial electron transfer.

Titanium Vacancies in TiO2 Nanofibers Enable Highly Efficient Photodriven Seawater Splitting.

Invited for the cover of this issue are Xiao-Yu Yang and co-workers at Wuhan University of Technology, Heinrich-Heine-Universität Düsseldorf, University of the Witwatersrand, and Ben-Gurion University of the Negev. The image depicts Ti vacancies in TiO2 as powerful drivers of photo- and photo-electrocatalytic seawater splitting for hydrogen production. Read the full text of the article at 10.1002/chem.202101817.

Interrogating the effects of ion-implantation-induced defects on the energy storage properties of bulk molybdenum disulphide.

The effects of implanted molybdenum and tungsten ions on the energy-storage properties of electrodes made from bulk molybdenum disulphide (MoS2) have been investigated. Six samples of crystalline MoS2 were modified by an ion-implantation strategy: three samples with Mo ions and three with W ions, at varying fluences and at an energy of 10 keV. The Stopping and Range of Ions in Matter (SRIM) software was used to determine the simulated defect density in terms of vacancies and the implanted ion-penetration depth. Raman spectroscopy and photoluminescence spectroscopy were used to determine any changes in the material as a result of irradiation. Electrochemistry showed that the ion-implanted MoS2 samples exhibited significant energy storage properties (such as capacity, cycling stability, coulombic efficiency, and electron transfer kinetics) compared to the pristine MoS2 samples, confirming the effects of defects induced by ion-implantation.

Microwave-enhanced electrochemical cycling performance of the LiNi0.2Mn1.8O4 spinel cathode material at elevated temperature.

The well-established poor electrochemical cycling performance of the LiMn2O4 (LMO) spinel cathode material for lithium-ion batteries at elevated temperature stems from the instability of the Mn(3+) concentration. In this work, a microwave-assisted solid-state reaction has been used to dope LMO with a very low amount of nickel (i.e., LiNi0.2Mn1.8O4, herein abbreviated as LMNO) for lithium-ion batteries from Mn3O4 which is prepared from electrolytic manganese oxide (EMD, γ-MnO2). To establish the impact of microwave irradiation on the electrochemical cycling performance at an elevated temperature (60 °C), the Mn(3+) concentration in the pristine and microwave-treated LMNO samples was independently confirmed by XRD, XPS, (6)LiMAS-NMR and electrochemical studies including electrochemical impedance spectroscopy (EIS). The microwave-treated sample (LMNOmic) allowed for the clear exposure of the {111} facets of the spinel, optimized the Mn(3+) content, promoting structural and cycle stability at elevated temperature. At room temperature, both the pristine (LMNO) and microwave-treated (LMNOmic) samples gave comparable cycling performance (>96% capacity retention and ca. 100% coulombic efficiency after 100 consecutive cycling). However, at an elevated temperature (60 °C), the LMNOmic gave an improved cycling stability (>80% capacity retention and ca. 90% coulombic efficiency after 100 consecutive cycling) compared to the LMNO. For the first time, the impact of microwave irradiation on tuning the average manganese redox state of the spinel material to enhance the cycling performance of the LiNi0.2Mn1.8O4 at elevated temperature and lithium-ion diffusion kinetics has been clearly demonstrated.

A Solid-State Electrolyte Based on Li0.95 Na0.05 FePO4 for Lithium Metal Batteries.

Solid-state electrolytes (SSEs) play a crucial role in developing lithium metal batteries (LMBs) with high safety and energy density. Exploring SSEs with excellent comprehensive performance is the key to achieving the practical application of LMBs. In this work, the great potential of Li0.95 Na0.05 FePO4 (LNFP) as an ideal SSE due to its enhanced ionic conductivity and reliable stability in contact with lithium metal anode is demonstrated. Moreover, LNFP-based composite solid electrolytes (CSEs) are prepared to further improve electronic insulation and interface stability. The CSE containing 50 wt% of LNFP (LNFP50) shows high ionic conductivity (3.58 × 10-4 S cm-1 at 25 °C) and good compatibility with Li metal anode and cathodes. Surprisingly, the LMB of Li|LNFP50|LiFePO4 cell at 0.5 C current density shows good cycling stability (151.5 mAh g-1 for 500 cycles, 96.5% capacity retention, and 99.3% Coulombic efficiency), and high-energy LMB of Li|LNFP50|Li[Ni0.8 Co0.1 Mn0.1 ]O2 cell maintains 80% capacity retention after 170 cycles, which are better than that with traditional liquid electrolytes (LEs). This investigation offers a new approach to commercializing SSEs with excellent comprehensive performance for high-performance LMBs.

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.

Enhanced methanol oxidation and oxygen reduction reactions on palladium-decorated FeCo@Fe/C core-shell nanocatalysts in alkaline medium.

Palladium based nano-alloys are well known for their unique electrocatalytic properties. In this work, a palladium-decorated FeCo@Fe/C core-shell nanocatalyst has been prepared by a new method called microwave-induced top-down nanostructuring and decoration (MITNAD). This simple, yet efficient technique, resulted in the generation of sub-10 nm sized FeCo@Fe@Pd nanocatalysts (mainly 3-5 nm) from a micron-sized (0.21-1.5 µm) FeCo@Fe/C. The electrocatalytic activities of the core-shell nanocatalysts were explored for methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline medium. A negative shift of 300 mV in the onset potential for MOR was observed, with a current thrice that of the Pd/C catalysts. A very low resistance to electron transfer (Rct) was observed while the ratio of forward-to-backward oxidation current (If/Ib) was doubled. The overpotential of ORR was significantly reduced with a positive shift of about 250 mV and twice the reduction current density was observed in comparison with Pd/C nanocatalysts with the same mass loading. The kinetic parameters (in terms of the Tafel slope (b) = -59.7 mV dec(-1) (Temkin isotherm) and high exchange current density (jo) = 1.26 × 10(-2) mA cm(-2)) provide insights into the favorable electrocatalytic performance of the catalysts in ORR in alkaline media. Importantly, the core-shell nanocatalyst exhibited excellent resistance to possible methanol cross-over during ORR, which shows excellent promise for application in direct alkaline alcohol fuel cells (DAAFCs).

Electrochemical Immunosensor for Ultra-Low Detection of Human Papillomavirus Biomarker for Cervical Cancer.

Human papillomavirus (HPV) is the causative agent for cervical cancer. Of the various types of HPV, the high-risk HPV-16 type is the most important antigenic high-risk HPV. In this work, the antigenic HPV-16 L1 peptide was immobilized on a glassy carbon electrode and used to detect several concentrations of the anti-HPV-16 L1 antibody, and vice versa. Two electrode platforms were used: onion-like carbon (OLC) and its polyacrylonitrile (OLC-PAN) composites. Both platforms gave a wide linear concentration range (1.95 fg/mL to 6.25 ng/mL), excellent sensitivity (>5.2 µA/log ([HPV-16 L1, fg/mL]), and extra-ordinarily low limit of detection (LoD) of 1.83 fg/mL (32.7 aM) and 0.61 fg/mL (10.9 aM) for OLC-PAN and OLC-based immunosensors, respectively. OLC-PAN modified with the HPV-16 L1 protein showed low LoD for the HPV-16 L1 antibody (2.54 fg/mL, i.e., 45.36 aM), proving its potential use for screening purposes. The specificity of detection was proven with the anti-ovalbumin antibody (anti-OVA) and native ovalbumin protein (OVA). An immobilized antigenic HPV-16 L1 peptide showed insignificant interaction with anti-OVA in contrast with the excellent interaction with anti-HPV-16 L1 antibody, thus proving high specificity. The application of the immunosensor as a potential point-of-care (PoC) diagnostic device was investigated with screen-printed carbon electrodes, which detected ultra-low (ca. 0.7 fg/mL ≈ 12.5 aM) and high (ca. 12 µg/mL ≈ 0.21 µM) concentrations. This study represents the lowest LoD reported for HPV-16 L1. It opens the door for further investigation with other electrode platforms and realization of PoC diagnostic devices for screening and testing of HPV biomarkers for cervical cancer.

Stoichiometry design in hierarchical CoNiFe phosphide for highly efficient water oxidation.

Rational composition design of trimetallic phosphide catalysts is of significant importance for enhanced surface reaction and efficient catalytic performance. Herein, hierarchical Co x Ni y Fe z P with precise control of stoichiometric metallic elements (x:y:z = (1-10):(1-10):1) has been synthesized, and Co1.3Ni0.5Fe0.2P, as the most optimal composition, exhibits remarkable catalytic activity (η = 320 mV at 10 mA cm-2) and long-term stability (ignorable decrease after 10 h continuous test at the current density of 10 mA cm-2) toward oxygen evolution reaction (OER). It is found that the surface P in Co1.3Ni0.5Fe0.2P was replaced by O under the OER process. The density function theory calculations before and after long-term stability tests suggest the clear increasing of the density of states near the Fermi level of Co1.3Ni0.5Fe0.2P/Co1.3Ni0.5Fe0.2O, which could enhance the OH- adsorption of our electrocatalysts and the corresponding OER performance. Electronic Supplementary Material: Supplementary material is available in the online version of this article at 10.1007/s40843-022-2061-x.

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.

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

[This corrects the article DOI: 10.1039/D2NA00455K.].

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.

Hierarchically fractal Co with highly exposed active facets and directed electron-transfer effect.

Hierarchically fractal Co with highly exposed active (002) facets, possessing a higher work function and more moderate hydrogen adsorption free energy, has been synthesized via a template-free self-assembly method for the directed electron-transfer design of HER catalysts. It shows a great improvement in the HER activity in comparison with that of nanostructured Co.

Onion-like Carbons Provide a Favorable Electrocatalytic Platform for the Sensitive Detection of Tramadol Drug.

This work reports the first study on the possible application of nanodiamond-derived onion-like carbons (OLCs), in comparison with conductive carbon black (CB), as an electrode platform for the electrocatalytic detection of tramadol (an important drug of abuse). The physicochemical properties of OLCs and CB were determined using X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET), and thermogravimetric analysis (TGA). The OLC exhibits, among others, higher surface area, more surface defects, and higher thermal stability than CB. From the electrochemical analysis (interrogated using cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy), it is shown that an OLC-modified glassy carbon electrode (GCE-OLC) allows faster electron transport and electrocatalysis toward tramadol compared to a GCE-CB. To establish the underlying science behind the high performance of the OLC, theoretical calculations (density functional theory (DFT) simulations) were conducted. DFT predicts that OLC allows for weaker surface binding of tramadol (E ad = -26.656 eV) and faster kinetic energy (K.E. = -155.815 Ha) than CB (E ad = -40.174 eV and -305.322 Ha). The GCE-OLC shows a linear calibration curve for tramadol over the range of ∼55 to 392 µM, with high sensitivity (0.0315 µA/µM) and low limit of detection (LoD) and quantification (LoQ) (3.8 and 12.7 µM, respectively). The OLC-modified screen-printed electrode (SPE-OLC) was successfully applied for the sensitive detection of tramadol in real pharmaceutical formulations and human serum. The OLC-based electrochemical sensor promises to be useful for the sensitive and accurate detection of tramadol in clinics, quality control, and routine quantification of tramadol drugs in pharmaceutical formulations.

Platinum Nanocatalysts Supported on Defective Hollow Carbon Spheres: Oxygen Reduction Reaction Durability Studies.

The durability and long-term applicability of catalysts are critical parameters for the commercialization and adoption of fuel cells. Even though a few studies have been conducted on hollow carbon spheres (HCSs) as supports for Pt in oxygen reduction reactions (ORR) catalysis, in-depth durability studies have not been conducted thus far. In this study, Pt/HCSs and Pt/nitrogen-doped HCSs (Pt/NHCSs) were prepared using a reflux deposition technique. Small Pt particles were formed with deposition on the outside of the shell and inside the pores of the shell. The new catalysts demonstrated high activity (>380 µA cm-2 and 240 mA g-1) surpassing the commercial Pt/C by more than 10%. The catalysts demonstrated excellent durability compared to a commercial Pt/C in load cycling, experiencing less than 50% changes in the mass-specific activity (MA) and surface area-specific activity (SA). In stop-start durability cycling, the new materials demonstrated high stability with more than 50% retention of electrochemical active surface areas (ECSAs). The results can be rationalised by the high BET surface areas coupled with an array of meso and micropores that led to Pt confinement. Further, pair distribution function (PDF) analysis of the catalysts confirmed that the nitrogen and oxygen functional groups, as well as the shell curvature/roughness provided defects and nucleation sites for the deposition of the small Pt nanoparticles. The balance between graphitic and diamond-like carbon was critical for the electronic conductivity and to provide strong Pt-support anchoring.