Photoactive materials based on semiconducting nanocarbons——A challenge opening new possibilities for photocatalysis

This perspective paper introduces the concept that nanocarbons and related materials such as carbon dots are an interesting intrinsic photocatalytic semiconducting material, and not only a modifier of the existing (semiconducting) materials to prepare hybrid materials. The semiconducting properties of the nanocarbons, and the possibility to have the band gap within the visible-light region through defect band engineering, introduction of light heteroatoms and control/manipulation of the curvature or surface functionalization are discussed. These materials are conceptually different from the 'classical' semiconducting photocatalysts, because semiconductor domains with tuneable characteristics are embedded in a conductive carbon matrix, with the presence of various functional groups (as C=0 groups) enhancing charge separation by trapping electrons. These nanocarbons open a range of new possibilities for photocatalysis both for energetic and environmental applications. The use of nanocarbons as quantum dots and photo luminescent materials was also analysed. (C) 2017 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A review of nanocarbons in energy electrocatalysis: Multifunctional substrates and highly active sites

Nanocarbons are of progressively increasing importance in energy electrocatalysis, including oxygen reduction, oxygen evolution, hydrogen evolution, COreduction, etc. Precious-metal-free or metal-free nanocarbon-based electrocatalysts have been revealed to potentially have effective activity and remarkable durability, which is promising to replace precious metals in some important energy technologies,such as fuel cells, metal–air batteries, and water splitting. In this review, rather than overviewing recent progress completely, we aim to give an in-depth digestion of present achievements, focusing on the different roles of nanocarbons and material design principles. The multifunctionalities of nanocarbon substrates(accelerating the electron and mass transport, regulating the incorporation of active components,manipulating electron structures, generating confinement effects, assembly into 3 D free-standing electrodes) and the intrinsic activity of nanocarbon catalysts(multi-heteroatom doping, hierarchical structure,topological defects) are discussed systematically, with perspectives on the further research in this rising research field. This review is inspiring for more insights and methodical research in mechanism understanding, material design, and device optimization, leading to a targeted and high-efficiency development of energy electrocatalysis.

Plasma activation towards oxidized nanocarbons for efficient electrochemical synthesis of hydrogen peroxide

Oxidized nanocarbons(ONCs)have been regarded as efficient electrocatalysts for H2O2 production.However,wet chemical procedures involving large volumes of strong acid and long synthetic time are usually needed to obtain these ONCs.Herein,a plasma activation strategy is developed as a rapid and environmentally benign approach to obtain various ONCs,including oxidized multiwalled carbon nanotubes,single-walled carbon nanotube,graphene,and super P carbon black.After a few minutes of plasma activation,oxygen-containing functional groups and defects can be effectively introduced onto the surface of nanocarbons.Enhanced electrocatalytic activity and selectivity are demonstrated by the plasma-ONCs for H2O2 production.Taking oxidized multiwalled carbon nanotubes as an example,high selectivity(up to 95%)and activity(0.75 V at 1 mA cm^(−2))can be achieved in alkaline solution.Moreover,ex situ x-ray photoelectron spectroscopy and in situ Raman measurements reveal that C–O,C=O,edge defect,and sp2 basal planar defect are probably the active sites.

The Porous Nanocarbons with Polynuclear Aromatic Cores

Three porous nanocarbons,1–3 that comprise pyrene,corannulene,and coronene cores encircled by cyclo-meta-phenylene(CMP)interconnections,have been synthesized and characterized.The interconnected CMPs caused different curvatures of the cores and imparted high solubility,large bathochromic shift,strong fluorescence,and low reduction potential to the systems.In solution,these porous nanocarbons existed as a complex mixture of dynamic processes that certainly influenced one another within any single molecule,leading to a set of rather simple proton nuclear magnetic resonance(^(1)H NMR)spectra.Single crystal X-ray diffraction and computational minimum energy analysis revealed the boatand saddle-like conformations of 1–3 in the solid state,significantly deviating from their conformations on the Au(111)surface.Furthermore,both 1 and 2 could form 2:1 complexes with C_(60),accompanied by adaptive geometry changes.In addition,1 served as a sky-blue emitter for an organic light-emitting diode(OLED).This work gives access and insights into a model system consisting of porous nanocarbons with intriguing supramolecular and optoelectronic properties.

Electrochemical manufacturing of nanocarbons from carbon dioxide in molten alkali metal carbonate salts： roles of alkali metal cations

One simple and fast way to manufacture a useful product from CO2 is to capture the gas by, and then carry out electrolysis in molten alkali metal carbonates. Carbon electro-deposition in molten Li2CO3-Na2CO3- KaCO3 （molar ratio： 43.5：31.5：25.0） has been widely reported in literature. However, studies in each of the individual alkali metal carbonates either have received less attention or are simply lacking in literature. Electrochem- ical studies of these molten carbonates are important to understand their underlying processes and reactions during the electrolysis. In this work, cyclic voltammograms （CVs） were recorded in each of the above-mentioned molten alkali carbonate salts using a 0.25 mm diameter Pt wire working electrode. In molten Na2CO3 and K2CO3, the main cathodic reaction was likely the formation of alkali metal, while that in Li2CO3 was carbon deposition. The results also suggest that other competing reactions such as CO and alkali metal carbide formation are possible as well in dif- ferent molten salts. On the CVs, the anodic current peaks observed are mostly associated with the oxidation of cathodic products. Flake/ring/sheet-like structures and quasi-spherical particles were observed in the produced carbon. The morphology of the carbon contained both amorphous and graphitic structures, which varied with different electrolysis variables.

Efficacy and prognostic analysis of carbon nanotracers combined with the da Vinci robot in the treatment of esophageal cancer

BACKGROUND Traditional methods cannot clearly visualize esophageal cancer(EC)tumor contours and metastases,which limits the clinical application of da Vinci robotassisted surgery.AIM To investigate the efficacy of the da Vinci robot in combination with nanocarbon lymph node tracers in radical surgery of EC.METHODS In total,104 patients with early-stage EC who were admitted to Liuzhou worker's Hospital from January 2020 to June 2023 were enrolled.The patients were assigned to an observation group(n=52),which underwent da Vinci robot-assisted minimally invasive esophagectomy(RAMIE)with the intraoperative use of nanocarbon tracers,and a control group(n=52),which underwent traditional surgery treatment.The operation time,intraoperative blood loss,postoperative drainage tube indwelling time,hospital stay,number of lymph nodes dissected,incidence of complications,and long-term curative effects were comparatively analyzed.The postoperative stress response C-reactive protein(CRP),cortisol,epinephrine(E)and inflammatory response interleukin(IL)-6,IL-8,IL-10,and tumor necrosis factor-alpha(TNF-α)were evaluated.RESULTS Compared with the control group,the observation group had significantly lower postoperative CRP,cortisol,and E levels(P<0.05)with a milder inflammatory response,as indicated by lower IL-6,IL-10,and TNF-αlevels(P<0.05).Patients who underwent RAMIE had less intraoperative blood loss and shorter operation times and hospital stays than those who underwent traditional surgery.The average number of dissected lymph nodes,time of lymph node dissection,and mean smallest lymph node diameter were all significantly lower in the observation group(P<0.05).The rate of postoperative complications was 5.77%in the observation group,significantly lower than the 15.38%observed in the control group.Furthermore,the lymphatic metastasis rate,reoperation rate,and 12-and 24-month cumulative mortality in the observation group were 1.92%,0%,0%,and 0%,respectively,all of which were significantly lower than those in the control group(P<0.05).CONCLUSION The treatment of EC using the da Vinci robot combined with nanocarbon lymph node tracers can achieve good surgical outcomes and demonstrates promising clinical applications.

Porous nitrogen/halogen dual-doped nanocarbons derived from imidazolium functionalized cationic metal-organic frameworks for highly efficient oxygen reduction reaction

Heteroatom-doped carbon materials as alternative catalysts for oxygen reduction reaction(ORR)have drawn increasing attention due to their tunable chemical and electronic structures for achieving high activity and stability. However, there still remains a great challenge to fabricate porous heteroatoms dual-doped carbons with uniformly doping in a facile and controllable way. Herein,imidazole/imidazolium-functionalized metal-organic frameworks(MOFs) are employed as precursors and templates to achieve porous nitrogen and halogen dual-doped nanocarbons. Among these carbon materials, the as-prepared nitrogen/bromine dual-doped catalyst BrNC-800 exhibits the best ORR performance with a positive half-wave potential at 0.80 V(vs. RHE) in 0.1 mol L-1 KOH, which is comparable to the benchmark commercial 20 wt% Pt/C catalyst. BrNC-800 shows excellent long term stability and methanol tolerance.This work provides a facile approach to fabricate highly efficient heteroatoms dual-doped carbon catalysts for energy conversion.

Fluoridation routes,function mechanism and application of fluorinated/fluorine-doped nanocarbon-based materials for various batteries:A review

With the popularity and widespread applications of electronics,higher demands are being placed on the performance of battery materials.Due to the large difference in electronegativity between fluorine and carbon atoms,doping fluorine atoms in nanocarbon-based materials is considered an effective way to improve the performance of used battery.However,there is still a blank in the systematic review of the mechanism and research progress of fluorine-doped nanostructured carbon materials in various batteries.In this review,the synthetic routes of fluorinated/fluorine-doped nanocarbon-based(CF_x)materials under different fluorine sources and the function mechanism of CF_x in various batteries are reviewed in detail.Subsequently,judging from the dependence between the structure and electrochemical performance of nanocarbon sources,the progress of CF_x based on different dimensions(0D–3D)for primary battery applications is reviewed and the balance between energy density and power density is critically discussed.In addition,the roles of CF_x materials in secondary batteries and their current applications in recent years are summarized in detail to illustrate the effect of introducing F atoms.Finally,we envisage the prospect of CF_x materials and offer some insights and recommendations to facilitate the further exploration of CF_x materials for various high-performance battery applications.

Identification of the Intrinsic Dielectric Properties of Metal Single Atoms for Electromagnetic Wave Absorption

Atomically dispersed metals on N-doped carbon supports(M-N_(xCs)) have great potential applications in various fields.However,a precise understanding of the definitive relationship between the configuration of metal single atoms and the dielectric loss properties of M-N_(xCs) at the atomic-level is still lacking.Herein,we report a general approach to synthesize a series of three-dimensional(3D)honeycomb-like M-N_xC(M=Mn,Fe,Co,Cu,or Ni) containing metal single atoms.Experimental results indicate that 3D M-N_(xCs) exhibit a greatly enhanced dielectric loss compared with that of the NC matrix.Theoretical calculations demonstrate that the density of states of the d orbitals near the Fermi level is significantly increased and additional electrical dipoles are induced due to the destruction of the symmetry of the local microstructure,which enhances conductive loss and dipolar polarization loss of 3D M-N_(xCs),respectively.Consequently,these 3D M-N_(xCs) exhibit excellent electromagnetic wave absorption properties,outperforming the most commonly reported absorbers.This study systematically explains the mechanism of dielectric loss at the atomic level for the first time and is of significance to the rational design of high-efficiency electromagnetic wave absorbing materials containing metal single atoms.

Sicilian serpentinite xenoliths containing abiotic organics with nanodiamond clusters as key model for prebiotic processes

Rock fragments from the deepest parts of a buried hydrothermal system belonging to the Mesozoic Tethys Ocean entered as xenoliths in a Miocenic diatreme,hence brought to the surface,in the Hyblean Plateau(Sicily).Some xenoliths consist of strongly serpentinized ultramafic rocks bearing blebs of abiotic organic matter,where clusters of amorphous carbon nanoparticles,including nanodiamonds,are immersed.Such an occurrence conjures up established hypotheses that diamond surfaces are suitable catalytic platforms stimulating the assemblage of complex bio-organic molecules relevant to the emergence of life on Earth.The appearance of bio-organic molecules under primitive Earth conditions is one of the major unsolved questions on the origin of life.Here we report new micro-Raman spectra on blebs of abiotic organic matter from a selected xenolith.Diamond bands were related to hydrogenated nanocrystalline diamonds,with size of nearly 1-1.6 nm,formed from organics at low pressures and temperatures.In particular,diamond surfaces can give rise to crystalline interfacial water layers that may have played a fundamental role in the early biosphere evolution as a good medium for rapidly transporting positive charges in the form of hydrated protons.Nowadays,proton gradients in alkaline hydrothermal vents along oceanic ridges are generally viewed as key pre-biotic factors.In general,serpentinites span the entire geological record,including prebiotic times.These hydrous ultramafic rocks often display evidence of abiotic carbon species,both organic and inorganic,including nanodiamonds,being also capable to give rise to chemiosmotic processes and proton gradients necessary to the organisms,such as the"Last Universal Common Ancestor"(LUCA),in the prebiotic Earth.

Nanocarbon-Enhanced 2D Photoelectrodes:A New Paradigm in Photoelectrochemical Water Splitting

Solar-driven photoelectrochemical(PEC)water splitting systems are highly promising for converting solar energy into clean and sustainable chemical energy.In such PEC systems,an integrated photoelectrode incorporates a light harvester for absorbing solar energy,an interlayer for transporting photogenerated charge carriers,and a co-catalyst for triggering redox reactions.Thus,understanding the correlations between the intrinsic structural properties and functions of the photoelectrodes is crucial.Here we critically examine various 2D layered photoanodes/photocathodes,including graphitic carbon nitrides,transition metal dichalcogenides,layered double hydroxides,layered bismuth oxyhalide nanosheets,and MXenes,combined with advanced nanocarbons(carbon dots,carbon nanotubes,graphene,and graphdiyne)as co-catalysts to assemble integrated photoelectrodes for oxygen evolution/hydrogen evolution reactions.The fundamental principles of PEC water splitting and physicochemical properties of photoelectrodes and the associated catalytic reactions are analyzed.Elaborate strategies for the assembly of 2D photoelectrodes with nanocarbons to enhance the PEC performances are introduced.The mechanisms of interplay of 2D photoelectrodes and nanocarbon co-catalysts are further discussed.The challenges and opportunities in the field are identified to guide future research for maximizing the conversion efficiency of PEC water splitting.

A perspective on carbon materials for future energy application

Nanocarbon materials play a critical role in the development of new or improved technologies and devices for sustainable production and use of renewable energy. This perspective paper defines some of the trends and outlooks in this exciting area, with the effort of evidencing some of the possibilities offered from the growing level of knowledge, as testified from the exponentially rising number of publications, and putting bases for a more rational design of these nanomaterials. The basic members of the new carbon family are fullerene, graphene, and carbon nanotube. Derived from them are carbon quantum dots, nanohorn, nanofiber, nano ribbon, nanocapsulate, nanocage and other nanomorphologies. Second generation nanocarbons are those which have been modified by surface functionalization or doping with heteroatoms to create specific tailored properties. The third generation of nanocarbons is the nanoarchitectured supramolecular hybrids or composites of the first and second genera- tion nanocarbons, or with organic or inorganic species. The advantages of the new carbon materials, relating to the field of sustainable energy, are discussed, evidencing the unique properties that they offer for developing next generation solar devices and energy storage solutions.

Defect and Doping Co‑Engineered Non‑Metal Nanocarbon ORR Electrocatalyst

Exploring low-cost and earth-abundant oxygen reduction reaction(ORR)electrocatalyst is essential for fuel cells and metal–air batteries.Among them,non-metal nanocarbon with multiple advantages of low cost,abundance,high conductivity,good durability,and competitive activity has attracted intense interest in recent years.The enhanced ORR activities of the nanocarbons are normally thought to originate from heteroatom(e.g.,N,B,P,or S)doping or various induced defects.However,in practice,carbon-based materials usually contain both dopants and defects.In this regard,in terms of the co-engineering of heteroatom doping and defect inducing,we present an overview of recent advances in developing non-metal carbon-based electrocatalysts for the ORR.The characteristics,ORR performance,and the related mechanism of these functionalized nanocarbons by heteroatom doping,defect inducing,and in particular their synergistic promotion effect are emphatically analyzed and discussed.Finally,the current issues and perspectives in developing carbon-based electrocatalysts from both of heteroatom doping and defect engineering are proposed.This review will be beneficial for the rational design and manufacturing of highly efficient carbon-based materials for electrocatalysis.

Electrocatalytic conversion of CO_2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO2 to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO2 solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube （CNT） type materials, long C-chain products （in particular isopropanol under optimized conditions, but also hydrocarbons up to C8-C9） were obtained from the reduction of CO2. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO2 are part of a photoelectrocatalytic （PEC） solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO2 to fuels and chemicals. The CO2 reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions （i.e. H2）.

Lymph node mapping in rabbit liver cancer with nanocarbon and methylene blue injecta

Objective:To discuss the value of lymph node mapping in rabbit liver cancer with nanocarbon and methylene blue injecta.Methods:Rabbit liver cancer model was established by transplanting VX2 cells with laparotomy in celiac planting method.Twenty Japan white rabbits were divided into two groups randomly.Each group had 10 rabbits.Lymph node mapping in (wo groups rabbit liver cancer were observed.Two groups rabbit liver cancer and local lymph nodes were removed.The number and location of local lymph nodes were recorded,and then the samples were obtained from both groups.Results:The lymph nodes dyed time was(100.50±29.92) s in nanocarbon group,and(11.20+4.18) s in methylene blue group with statistical significance between two groups(P=0.000).In the comparison of lymph node fading time,nanocarbon group was(2.22±0.74) h,methylene blue group was(1.63+0.54) h,nanocarbon group was longer than the methylene blue group,but without statistical significance(P=0.058).The accuracy was 87.5% (35/40) in methylene blue group,while,the nanocarbon group was 87.2%(34/39),with statistical significance(P=1.000).Conclusions:Experimental results show that application of nanocarbon injection and methylene blue injection during resection of liver cancer and local lymph nodes in rabbit liver cancer model has obvious tracer function in liver cancer and lymphatic drainage. It can reduce the complexity and risk of the operation,and avoid the blindness in the process of traditional lymph node dissection surgery.Besides,they can effectively reduce the number of residual lymph nodes after operation.It can achieve the lymph node dissection more thoroughly, promptly,easily and safely.

Palladium nanoclusters immobilized on defective nanodiamond-graphene core-shell supports for semihydrogenation of phenylacetylene

We report a nanocarbon material with nanodiamond(ND) core and graphene shell(ND@G) as a support for Pd nanocatalysts. The designed catalyst performed good selectivity of styrene(85.2%) at full conversion of phenylacetylene and superior stability under mild conditions. Supported Pd catalysts are characterized by means of high resolution transmission electron microscopy(HRTEM), Raman, X-ray diffraction(XRD), X-ray photoelectron spectroscopy(XPS) and H2 temperature-programmed reduction(H2-TPR).The results clearly show that formation of the strong metal-support interaction(SMSI) between Pd nanoclusters and the defective graphene shell helpfully modifies the selectivity and stability of the Pd-based catalysts.

Recent developments of nanocarbon based supports for PEMFCs electrocatalysts

Nanocarbons,widely and commonly used as supports for supported Pt-based electrocatalysts in PEMFCs,play a significant role in Pt dispersion and accessibility,further determining their corresponding electrocatalytic performance.This paper provides an overview of the nanoarchitectures and surface physicochemical properties of nanocarbons affecting the electrocatalyst performance,with an emphasis on both physical characteristics,including pore structure,and chemical properties,including heteroatom doping and functional carbon-based supports.This review discusses the recent progress in nanocarbon supports,guides the future development direction of PEMFC supports,and provides our own viewpoints for the future research and design of PEMFCs catalysts,advancing the commercialization of PEMFCs.

Full-faradaic-active nitrogen species doping enables high-energy-density carbon-based supercapacitor

Nitrogen doping is usually adopted in carbon based supercapacitor to enhance its relatively low energy density by providing extra pseudocapacity.However,the improvement of energy density is normally limited because the content of the introduced nitrogen species is not high and meanwhile only part of them is electrochemically active.Herein,we designed and fabricated a class of hierarchical nitrogen-rich porous carbons(HNPCs)possessing not only very high nitrogen content(up to 21.7 atom%)but also fully electrochemically active nitrogen species(i.e.,pyridinic N,pyrrolic N and oxidized N).Especially,in the synthesis of HNPCs,graphitic carbon nitride(g-C3N4)was used in situ not only as a nitrogen source but also as a catalyst to facilitate the polymerization of phenol and formaldehyde(as carbon precursor)and as a template to create the hierarchical porous structure.As electrodes for aqueous symmetric supercapacitor,the HNPCs with full faradaic-active nitrogen functionalities exhibit excellent supercapacitor performance:high energy density of 36.8 Wh/kg at 2.0 kW/kg(maintaining 25.7 Wh/kg at 38 kW/kg),superior rate capability with 78%capacitance retention from 1.0 to 20 A/g and excellent cycling stability with over95%capacitance retention after 10000 cycles,indicating their promising application potential in electrochemical energy storage.This novel carbon material with high-content and full electrochemically active nitrogen species may find extensive potential applications in the energy storage/conversion,catalysis,adsorption,and so on.

Azobenzene‑Based Solar Thermal Fuels:A Review

The energy storage mechanism of azobenzene is based on the transformation of molecular cis and trans isomerization,while NBD/QC,DHA/VHF,and fulvalene dimetal complexes realize the energy storage function by changing the molecular structure.Acting as“molecular batteries,”they can exhibit excellent charging and discharging behavior by converting between trans and cis isomers or changing molecular structure upon absorption of ultraviolet light.Key properties determining the performance of STFs are stored energy,energy density,half-life,and solar energy conversion efficiency.This review is aiming to provide a comprehensive and authoritative overview on the recent advancements of azobenzene molecular photoswitch system in STFs fields,including derivatives and carbon nano-templates,which is emphasized for its attractive performance.Although the energy storage performance of Azo-STFs has already reached the level of commercial lithium batteries,the cycling capability and controllable release of energy still need to be further explored.For this,some potential solutions to the cycle performance are proposed,and the methods of azobenzene controllable energy release are summarized.Moreover,energy stored by STFs can be released in the form of mechanical energy,which in turn can also promote the release of thermal energy from STFs,implying that there could be a relationship between mechanical and thermal energy in Azo-STFs,providing a potential direction for further research on Azo-STFs.

Nickel-catalyzed Construction of Heat Conductive Network in Electrically Calcined Anthracite (ECA) Based Carbon Blocks

Nickel nitrate was introduced into carbon blocks by using ECA aggregates as catalyst-carrier.The Ni-containing anthracite aggregates were firstly prepared by mixing anthracite aggregates in nickel nitrate ethanol solution and then incorporated into carbon blocks after pre-treating.The phase composition,microstructure and properties of all carbon blocks fired at 1 000℃or 1 400℃in a coke bed were studied with the aid of an X-ray diffractomer,a field emission scanning electron microscope,a mercury porosimetry and a laser thermal conductivity meter.The results showed that the addition of Ni-containing anthracite aggregates promoted the formation of one-dimensional nanocarbon andβ-SiC whiskers at 1 000℃and the growth ofβ-Sialon at 1 400℃,respectively.Moreover,the cold compressive strength and microporosity characteristics of the carbon blocks with the addition of Ni-containing anthracite aggregates were enhanced and the thermal conductivity was remarkably improved attributing to the high heat conductive network formed by the ceramic phases.