Highly Curved Nanostructure-Coated Co, N-Doped Carbon Materials for Oxygen Electrocatalysis.

Nitrogen-doped graphene could catalyze the electrochemical reduction and evolution of oxygen, but unfortunately suffers from sluggish catalytic kinetics. Herein, for the first time, we report an onion-like carbon coated Co, N-doped carbon (OLC/Co-N-C) material, which possesses multilayers of highly curved nanostructures that form mesoporous architectures. These unique nanospheres are produced when surfactant micelles are introduced to synthesis precursors. Owing to the combined electronic effect and nanostructuring effect, our OLC/Co-N-C materials exhibit high bifunctional oxygen reduction/evolution reaction (ORR/OER) activity, showing a promising application in rechargeable Zn-air batteries. Experimental results are rationalized by theoretical calculations, showing that the curvature of graphitic carbon plays a vital role in promoting activities of meta-carbon atoms near graphitic N and ortho/meta carbon atoms close to pyridinic N.

Hierarchically Nanoporous 3D Assembly Composed of Functionalized Onion-Like Graphitic Carbon Nanospheres for Anode-Minimized Li Metal Batteries.

Despite the recent attention for Li metal anode (LMA) with high theoretical specific capacity of ≈3860 mA h g-1 , it suffers from not enough practical energy densities and safety concerns originating from the excessive metal load, which is essential to compensate for the loss of Li sources resulting from their poor coulombic efficiencies (CEs). Therefore, the development of high-performance LMA is needed to realize anode-minimized Li metal batteries (LMBs). In this study, high-performance LMAs are produced by introducing a hierarchically nanoporous assembly (HNA) composed of functionalized onion-like graphitic carbon building blocks, several nanometers in diameter, as a catalytic scaffold for Li-metal storage. The HNA-based electrodes lead to a high Li ion concentration in the nanoporous structure, showing a high CE of ≈99.1%, high rate capability of 12 mA cm-2 , and a stable cycling behavior of more than 750 cycles. In addition, anode-minimized LMBs are achieved using a HNA that has limited Li content (≈0.13 mg cm-2 ), corresponding to 6.5% of the cathode material (commercial NCM622 (≈2 mg cm-2 )). The LMBs demonstrate a feasible electrochemical performance with high energy and power densities of ≈510 Wh kgelectrode -1 and ≈2760 W kgelectrode -1 , respectively, for more than 100 cycles.

Superior Electrochemical Properties of Nanofibers Composed of Hollow CoFe2 O4 Nanospheres Covered with Onion-Like Graphitic Carbon.

Nanofibers composed of hollow CoFe2 O4 nanospheres covered with onion-like carbon are prepared by applying nanoscale Kirkendall diffusion to the electrospinning process. Amorphous carbon nanofibers embedded with CoFe2 @onion-like carbon nanospheres are prepared by reduction of the electrospun nanofibers. Oxidation of the CoFe2 -C nanofibers at 300 °C under a normal atmosphere produces porous nanofibers composed of hollow CoFe2 O4 nanospheres covered with onion-like carbon. CoFe2 nanocrystals are transformed into the hollow CoFe2 O4 nanospheres during oxidation through a well-known nanoscale Kirkendall diffusion process. The discharge capacities of the carbon-free CoFe2 O4 nanofibers composed of hollow nanospheres and the nanofibers composed of hollow CoFe2 O4 nanospheres covered with onion-like carbon are 340 and 930 mA h g(-1) , respectively, for the 1000th cycle at a current density of 1 A g(-1) . The nanofibers composed of hollow CoFe2 O4 nanospheres covered with onion-like carbon exhibit an excellent rate performance even in the absence of conductive materials.

Evaluating the effect of unidirectional loading on the piezoresistive characteristics of carbon nanoparticles.

The piezoresistive effect of materials can be adopted for a plethora of sensing applications, including force sensors, structural health monitoring, motion detection in fabrics and wearable, etc. Although metals are the most widely adopted material for sensors due to their reliability and affordability, they are significantly affected by temperature. This work examines the piezoresistive performance of carbon nanoparticle (CNP) bulk powders and discusses their potential applications based on strain-induced changes in their resistance and displacement. The experimental results are correlated with the characteristics of the nanoparticles, namely, dimensionality and structure. This report comprehensively characterizes the piezoresistive behavior of carbon black (CB), onion-like carbon (OLC), carbon nanohorns (CNH), carbon nanotubes (CNT), dispersed carbon nanotubes (CNT-D), graphite flakes (GF), and graphene nanoplatelets (GNP). The characterization includes assessment of the ohmic range, load-dependent electrical resistance and displacement tracking, a modified gauge factor for bulk powders, and morphological evaluation of the CNP. Two-dimensional nanostructures exhibit promising results for low loads due to their constant compression-to-displacement relationship. Additionally, GF could also be used for high load applications. OLC's compression-to-displacement relationship fluctuates, however, for high load it tends to stabilize. CNH could be applicable for both low and high loading conditions since its compression-to-displacement relationship fluctuates in the mid-load range. CB and CNT show the most promising results, as demonstrated by their linear load-resistance curves (logarithmic scale) and constant compression-to-displacement relationship. The dispersion process for CNT is unnecessary, as smaller agglomerates cause fluctuations in their compression-to-displacement relationship with negligible influence on its electrical performance.

Concurrently boosted oxygen reduction/evolution electrocatalysis over highly loaded CoNi/onion-like carbon hybrid nanosheets.

Balancing the bicatalytic activities and stabilities between oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a critical yet challenging task for exploring advanced rechargeable Zinc-air batteries (ZABs). Herein, a hybrid nanosheet catalyst with highly dispersed and densified metallic species is developed to boost the kinetics and stabilities of both ORR and OER concurrently. Through a progressive coordination and pyrolysis approach, we directly prepared highly conductive onion-like carbon (OLC) accommodating dense ORR-active CoNC species and enveloping high-loading OER-active CoNi-synergic structures within a porous lamellar architecture. The resultant CoNi/OLC nanosheet catalyst delivers better ORR and OER activities showcasing a smaller reversible oxygen electrode index (ΔE = Ej10 - E1/2) of 0.71 V, compared to state-of-the-art Pt/C-RuO2 catalysts (0.75 V), Co/amorphous carbon polyhedrons (0.80 V), NiO nanoparticles with higher Ni loading (1.00 V), and most CoNi-based bifunctional catalysts reported so far. The rechargeable ZAB assembled with the developed catalyst achieves a remarkable peak power density of 270.3 mW cm-2 (172 % of that achieved by Pt/C + RuO2) and ultrahigh cycling stability with a negligible increase in voltage gap after 800 h (110 mV increase after 200 h for a Pt/C + RuO2-based battery), standing the top level of those ever reported.

Antibacterial Effect of Carbon Nanomaterials: Nanotubes, Carbon Nanofibers, Nanodiamonds, and Onion-like Carbon.

The increasing resistance of bacteria and fungi to antibiotics is one of the health threats facing humanity. Of great importance is the development of new antibacterial agents or alternative approaches to reduce bacterial resistance to available antibacterial drugs. Due to the complexity of their properties, carbon nanomaterials (CNMs) may be of interest for a number of biomedical applications. One of the problems in studying the action of CNMs on microorganisms is the lack of universally standardized methods and criteria for assessing antibacterial and antifungal activity. In this work, using a unified methodology, a comparative study of the antimicrobial properties of the CNM systemic kit against common opportunistic microorganisms, namely Escherichia coli and Staphylococcus aureus, was carried out. Multiwalled carbon nanotubes (MWNTs), catalytic filamentous carbon with different orientations of graphene blocks (coaxial-conical and stacked, CFC), ionic carbon (OLC), and ultrafine explosive nanodiamonds (NDs) were used as a system set of CNMs. The highest antimicrobial activity was shown by NDs, both types of CFCs, and carboxylated hydrophilic MWCNTs. The SEM results point out the difference between the mechanisms of action of UDD and CFC nanotubes.

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.

Lithiophilic onion-like carbon spheres as lithium metal uniform deposition host.

Lithium metal is considered as a promising anode material for next-generation secondary batteries, owing to its high theoretical specific capacity (3860 mA h g-1). Nevertheless, the practical application of Li in lithium metal batteries (LMBs) is hampered by inhomogeneous Li deposition and irreversible "dead Li", which lead to low coulombic efficiency (CE) and safe hazards. Designing unique lithiophilic structure is an efficient strategy to control Li uniformly plating /stripping. Here, we report the silver (Ag) nanoparticles coated with nitrogen-doped onion-like carbon microspheres (Ag@NCS) as a host to reduce the nucleation overpotential of Li for dendrite-free LBMs. The Ag@NCS were prepared by a simple one-step injection pyrolysis. The lithiophilic Ag is demonstrated to be priority selective deposition of Li in the carbon cage. Meanwhile, the onion-like structure benefits to uniform lithium nucleation and dendrite-free lithium during cycling. Impressively, we successfully captured lithium metal on different hosts at atomic scale, further proving that Ag@NCS can effectively and uniformly deposit Li. Besides, Ag@NCS show a superiorly electrochemical performance with a low nucleation overpotential (∼1 mV), high CE and stable cycling performance (over 400 cycles at 0.5 mA cm-2) compared to the Ag-free onion-like carbon in LMBs. Even under harsh conditions (1 mA cm-2, 4 mA h cm-2), Ag@NCS still present superior cycling stability for more than 150 cycles. Furthermore, a full cell composed of LiFePO4 cathode exhibits significantly improved voltage hysteresis with low voltage polarization. This work provides a new choice and route for the design and preparation of lithiophilic host materials.

The local electric field effect of onion-like carbon nanoparticles for improved laser desorption/ionization efficiency of saccharides.

It is still a challenge to improve ionization efficiency of saccharides in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). Herein, the highly curved onion-like carbon nanoparticles (OCS) were synthesized from the low-price candle raw via a facile strategy. The unique nanostructure of OCS showed large surface area with plentiful mesoporous architecture, highly curved sp2 carbon with regulating electronic effect, and good hydrophilicity, which could be beneficial to facilitate the desorption and ionization efficiency in MS process. The prepared OCS material as MALDI matrix exhibited the superior performance for the detection of xylose, glucose, maltose monohydrate, and raffinose pentahydrate in positive-ion mode with low background noise, enhanced ion intensities, uniform distribution, excellent reproducibility, good salt-tolerance, and high sensitivity compared to control candle soot (CS) and traditional α-cyano-4-hydroxycinnamic acid (CHCA) matrices. This highly effective LDI of OCS matrix was attributed to its enhancing local electric field effect, strong UV absorption ability, and high photo-thermal conversion performance. Furthermore, the OCS-assisted LDI MS approach was employed to quantitatively detect glucose in rat serum. This LDI MS platform may have valuable for the analysis of metabolites in clinical research.

Unlocking Zinc-Ion Energy Storage Performance of Onion-Like Carbon by Promoting Heteroatom Doping Strategy.

Onion-like carbon (OLC) is one kind of a quasi-nanosphere with a concentric graphite shell structure and abundant mesopores, which is appropriate for a high rate of charging/discharging and long-lifespan cycling. However, the moderate specific surface area seriously impeded its capacitance performance in comparison with activated carbon and porous carbon. Herein, we have unlocked the Zn ion storage performance of OLC material through introducing N and P dopants. Benefitting from the fabricated N,P-OLC with a fully accessible external surface area for ion adsorption, high proportion of mesopores for fast ion migration, and synergistic effect of N and P co-doping in a carbon matrix favoring chemical adsorption of Zn2+ ions, when applied as a cathode electrode for Zn ion hybrid supercapacitors (ZHSCs), such a device can deliver a high specific capacitance of 420.3 F g-1 (184.5 mA h g-1) at 0.5 A g-1, an outstanding capacitance retention capability of 262.7 F g-1 even at 20 A g-1 (∼63% capacitance retention), a high energy density of 149.5 W h kg-1, and a high power density of 26.7 kW kg-1. Furthermore, this N,P-OLC material can in situ tightly integrate with a carbon cloth (CC) or carbon fiber to construct a freestanding and flexible electrode. The fabricated Zn//N,P-OLC@CC device achieved a high energy density of 85.3 mW h cm-2, a high power density of 24.3 W cm-2, and a long-term cycling lifespan (77.8% after 50 000 cycles). At last, the assembled quasi-solid-state fiber-shaped ZHSCs also present excellent flexibility and practicality. Our study exhibits that OLC can act as a promising carbon electrode for ZHSCs.