Recent Progress in Multifunctional Graphene-Based Nanocomposites for Photocatalysis and Electrocatalysis Application.

The global energy shortage and environmental degradation are two major issues of concern in today's society. The production of renewable energy and the treatment of pollutants are currently the mainstream research directions in the field of photocatalysis. In addition, over the last decade or so, graphene (GR) has been widely used in photocatalysis due to its unique physical and chemical properties, such as its large light-absorption range, high adsorption capacity, large specific surface area, and excellent electronic conductivity. Here, we first introduce the unique properties of graphene, such as its high specific surface area, chemical stability, etc. Then, the basic principles of photocatalytic hydrolysis, pollutant degradation, and the photocatalytic reduction of CO2 are summarized. We then give an overview of the optimization strategies for graphene-based photocatalysis and the latest advances in its application. Finally, we present challenges and perspectives for graphene-based applications in this field in light of recent developments.

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.

SiC@FeZnZiF as a Bifunctional Catalyst with Catalytic Activating PMS and Photoreducing Carbon Dioxide.

Herein, we encapsulated modified silicon carbide nanoparticles utilizing a metal-organic backbone. E-SiC-FeZnZIF composites were successfully prepared via Fe doping. The catalysis activity of this bifunctional composite material was evaluated by the degradation of tetracycline (THC) and carbamazepine (CBZ) and the reduction of carbon dioxide (CO2). Nano SiC has received widespread attention in advanced oxidation applications, especially in the catalytic activation of peroxymonosulfate (PMS). However, the inferior activity of SiC has severely restricted its practical use. In this study of dual functional composite materials, nano SiC was firstly etched under aqueous alkali. Then, zeolite imidazolate frame-8 (ZIF-8) was used for immobilization. The filling of the etched nano SiC with FeZnZiF was confirmed by SEM, XRD, FTIR, BET, and XPS analyses. In addition, E-SiC-FeZnZIF exhibited excellent catalytic activation of peroxymonosulfate (PMS) to oxidize water pollutants, which can degrade tetracycline hydrochloride (THC), achieving a removal rate of 72% within 60 min. Moreover, E-SiC-FeZnZIF exhibited a relatively high CO2 reduction rate with H2O. The yields of CO and CH4 were 0.085 and 0.509 µmol g-1, respectively, after 2 h, which are higher than that of 50 nm of commercial SiC (CO: 0.084 µmol g-1; CH4: 0.209 µmol g-1). This work provides a relatively convenient synthesis path for constructing metal skeleton composites for advanced oxidation and photocatalytic applications. This will have practical significance in protecting water bodies and reducing CO2, which are vital not only for maintaining the natural ecological balance and negative feedback regulation, but also for creating a new application carrier based on nano silicon carbide.

Interfacial construction of P25/Bi2WO6 composites for selective CO2 photoreduction to CO in gas-solid reactions.

Photocatalysis provides an attractive approach to convert CO2 into valuable fuels, which relies on a well-designed photocatalyst with good selectivity and high CO2 reduction ability. Herein, a series of P25/Bi2WO6 nanocomposites were synthesized by a simple one-step in situ hydrothermal method. The formation of a heterojunction between Bi2WO6, which absorbs visible light, and P25, which absorbs ultraviolet light, expands the utilization of sunlight by the catalysts, and consequently, leads to a remarkably enhanced CO2 selective photoreduction to CO. The maximum CO yield of the P25/Bi2WO6 heterojunction under simulated solar irradiation was 15.815 µmol g-1 h-1, which was 4.04 and 2.80 times higher than that of pure P25 and Bi2WO6, respectively. Our investigations verified a Z-scheme charge migration mechanism based on various characterization techniques between P25 and Bi2WO6. Furthermore, in situ DRIFTS uncovered the related reaction intermediates and CO2 photoreduction mechanism. Our work sheds light on investigating the efficacious construction of Bi2WO6-based hybrids for light-driven photocatalysis.

Recent Progress in Graphene-Based Electrocatalysts for Hydrogen Evolution Reaction.

Hydrogen is regarded as a key renewable energy source to meet future energy demands. Moreover, graphene and its derivatives have many advantages, including high electronic conductivity, controllable morphology, and eco-friendliness, etc., which show great promise for electrocatalytic splitting of water to produce hydrogen. This review article highlights recent advances in the synthesis and the applications of graphene-based supported electrocatalysts in hydrogen evolution reaction (HER). Herein, powder-based and self-supporting three-dimensional (3D) electrocatalysts with doped or undoped heteroatom graphene are highlighted. Quantum dot catalysts such as carbon quantum dots, graphene quantum dots, and fullerenes are also included. Different strategies to tune and improve the structural properties and performance of HER electrocatalysts by defect engineering through synthetic approaches are discussed. The relationship between each graphene-based HER electrocatalyst is highlighted. Apart from HER electrocatalysis, the latest advances in water electrolysis by bifunctional oxygen evolution reaction (OER) and HER performed by multi-doped graphene-based electrocatalysts are also considered. This comprehensive review identifies rational strategies to direct the design and synthesis of high-performance graphene-based electrocatalysts for green and sustainable applications.

Construction of CoP/Co2P Coexisting Bifunctional Self-Supporting Electrocatalysts for High-Efficiency Oxygen Evolution and Hydrogen Evolution.

Development of a low cost, high activity, and stable nonprecious metal bifunctional catalyst for electrocatalytic water cracking is a hot topic and big challenge. In this paper, we prepared a nitrogen-doped carbon nanotube (NCNT)-enhanced three-dimensional self-supported electrocatalyst with CoP and Co2P coexistence by a two-step strategy of high-temperature carbonization and low-temperature phosphorylation. Furthermore, the induced three-dimensional carbon network skeleton facilitates rapid charge transfer. In addition, the active sites of the carbon foam (CF) are greatly increased by the construction of hollow structures. As a bifunctional electrocatalyst, CoP/Co2P/NCNT@CF exhibited excellent catalytic activity for both hydrogen evolution reaction and oxygen evolution reaction in alkaline media, requiring low overpotentials of 133 and 289 mV to obtain a current density of 10 mA cm-2, respectively. Additionally, the synthesized catalysts also exhibit good long-term stability, maintaining high catalytic activity after 20 h of continuous operation. We also confirmed the main driving force to improve the electron transfer between the heterostructures of Co and P by XPS spectra. The excellent electrocatalytic performance can be attributed to the close synergy between the highly active CoP/Co2P/NCNT and CF. This study provides a new strategy for the design of highly active bifunctional self-supporting electrocatalysts.

Preparation and Characterization of Multi-Doped Porous Carbon Nanofibers from Carbonization in Different Atmospheres and Their Oxygen Electrocatalytic Properties Research.

Recently, electrocatalysts for oxygen reduction reaction (ORR) as well as oxygen evolution reaction (OER) hinged on electrospun nanofiber composites have attracted wide research attention. Transition metal elements and heteroatomic doping are important methods used to enhance their catalytic performances. Lately, the construction of electrocatalysts based on metal-organic framework (MOF) electrospun nanofibers has become a research hotspot. In this work, nickel-cobalt zeolitic imidazolate frameworks with different molar ratios (NixCoy-ZIFs) were synthesized in an aqueous solution, followed by NixCoy-ZIFs/polyacrylonitrile (PAN) electrospun nanofiber precursors, which were prepared by a simple electrospinning method. Bimetal (Ni-Co) porous carbon nanofiber catalysts doped with nitrogen, oxygen, and sulfur elements were obtained at high-temperature carbonization treatment in different atmospheres (argon (Ar), Air, and hydrogen sulfide (H2S)), respectively. The morphological properties, structures, and composition were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Moreover, the specific surface area of materials and their pore size distribution was characterized by Brunauer-Emmett-Teller (BET). Linear sweep voltammetry curves investigated catalyst performances towards oxygen reduction and evolution reactions. Importantly, Ni1Co2-ZIFs/PAN-Ar yielded the best ORR activity, whereas Ni1Co1-ZIFs/PAN-Air exhibited the best OER performance. This work provides significant guidance for the preparation and characterization of multi-doped porous carbon nanofibers carbonized in different atmospheres.

N-Doped Graphenelike Nanostructures from p-Nitro Aniline-Based Foam: Formation, Structure, and Applications as a Nanofiller.

Production of snake foam based on p-nitro aniline (PNA) was considered fun in old-school chemistry laboratories. Herein, we report the fabrication of a new carbon nanomaterial from PNA-based foam. The resulting material, resembling graphene and consisting of nitrogen heteroatoms, is N-doped graphenelike nanostructures, and their morphology, structure, and stability are comprehensively examined using combined techniques including C-13 NMR spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). An optimized route was also established for their large-scale production. Further experimental validation of them as a nanofiller in polymer [SEBS (20 wt %) and paraffin wax (80 wt %)]-based nanocomposites was carried out, and we found that the thermomechanical properties of the nanocomposites were synchronously improved, which was attributed to the enshrouding effect of the nanofiller to the polymer chains. Owing to their good thermomechanical property and low-cost feature, these new nanomaterials can be further explored as a promising candidate for applications in energy storage, catalysis, and CO2 capture.