Photoactivated Fluorescence Enhancement in F,N‐Doped Carbon Dots with Piezochromic Behavior

Photoactivation in CdSe/ZnS quantum dots (QDs) on UV/Vis light exposure improves photoluminescence (PL) and photostability. However, it was not observed in fluorescent carbon quantum dots (CDs). Now, photoactivated fluorescence enhancement in fluorine and nitrogen co‐doped carbon dots (F,N‐doped CDs) is presented. At 1.0 atm, the fluorescence intensity of F,N‐doped CDs increases with UV light irradiation (5 s–30 min), accompanied with a blue‐shift of the fluorescence emission from 586 nm to 550 nm. F,N‐doped CDs exhibit photoactivated fluorescence enhancement when exposed to UV under high pressure (0.1 GPa). F,N‐doped CDs show reversible piezochromic behavior while applying increasing pressure (1.0 atm to 9.98 GPa), showing a pressure‐triggered aggregation‐induced emission in the range 1.0 atm–0.65 GPa. The photoactivated CDs with piezochromic fluorescence enhancement broadens the versatility of CDs from ambient to high‐pressure conditions and enhances their anti‐photobleaching.     

Large‐Scale Synthesis of MOF‐Derived Superporous Carbon Aerogels with Extraordinary Adsorption Capacity for Organic Solvents

Carbon aerogels (CAs) with 3D interconnected networks hold promise for application in areas such as pollutant treatment, energy storage, and electrocatalysis. In spite of this, it remains challenging to synthesize high‐performance CAs on a large scale in a simple and sustainable manner. We report an eco‐friendly method for the scalable synthesis of ultralight and superporous CAs by using cheap and widely available agarose (AG) biomass as the carbon precursor. Zeolitic imidazolate framework‐8 (ZIF‐8) with high porosity is introduced into the AG aerogels to increase the specific surface area and enable heteroatom doping. After pyrolysis under inert atmosphere, the ZIF‐8/AG‐derived nitrogen‐doped CAs show a highly interconnected porous mazelike structure with a low density of 24 mg cm^?3, a high specific surface area of 516 m² g^?1, and a large pore volume of 0.58 cm^?3 g^?1. The resulting CAs exhibit significant potential for application in the adsorption of organic pollutants.     

The Molecular Composition of Soot

Soot (sometimes referred to as black carbon) is produced when hydrocarbon fuels are burned. Our hypothesis is that polynuclear aromatic hydrocarbon (PAH) molecules are the dominant component of soot, with individual PAH molecules forming ordered stacks that agglomerate into primary particles (PP). Here we show that the PAH composition of soot can be exactly determined and spatially resolved by low‐fluence laser desorption ionization, coupled with high‐resolution mass spectrometry imaging. This analysis revealed that PAHs of 239–838 Da, containing few oxygenated species, comprise the soot observed in an ethylene diffusion flame. As informed by chemical graph theory (CGT), the vast majority of species observed in the sampled particulate matter may be described as benzenoids, consisting of only fused 6‐membered rings. Within that limit, there is clear evidence for the presence of radical PAH in the particulate samples. Further, for benzenoid structures the observed empirical formulae limit the observed isomers to those which are nearly circular with high aromatic conjugation lengths for a given aromatic ring count. These results stand in contrast to recent reports that suggest higher aliphatic composition of primary particles.     

Designing a 0D/2D S‐Scheme Heterojunction over Polymeric Carbon Nitride for Visible‐Light Photocatalytic Inactivation of Bacteria

Constructing heterojunctions between two semiconductors with matched band structure is an effective strategy to acquire high‐efficiency photocatalysts. The S‐scheme heterojunction system has shown great potential in facilitating separation and transfer of photogenerated carriers, as well as acquiring strong photoredox ability. Herein, a 0D/2D S‐Scheme heterojunction material involving CeO₂ quantum dots and polymeric carbon nitride (CeO₂/PCN) is designed and constructed by in situ wet chemistry with subsequent heat treatment. This S‐scheme heterojunction material shows high‐efficiency photocatalytic sterilization rate (88.1 %) towards Staphylococcus aureus (S. aureus) under visible‐light irradiation (λ≥420 nm), which is 2.7 and 8.2 times that of pure CeO₂ (32.2 %) and PCN (10.7 %), respectively. Strong evidence of S‐scheme charge transfer path is verified by theoretical calculations, in situ irradiated X‐ray photoelectron spectroscopy, and electron paramagnetic resonance.     

On‐Surface Synthesis of Cumulene‐Containing Polymers via Two‐Step Dehalogenative Homocoupling of Dibromomethylene‐Functionalized Tribenzoazulene

Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on‐surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well‐controlled ultrahigh‐vacuum conditions. Here we report the on‐surface synthesis of a polymer linked by cumulene‐like bonds on a Au(111) surface via sequential thermally activated dehalogenative C?C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene‐like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X‐ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on‐surface synthesis of cumulene‐containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces.     

A Blinking Mesoporous TiO2−x Composed of Nanosized Anatase with Unusually Long‐Lived Trapped Charge Carriers

A mesoporous TiO_2?x material comprised of small, crystalline, vacancy‐rich anatase nanoparticles (NPs) shows unique optical, thermal, and electronic properties. It is synthesized using polymer‐derived mesoporous carbon (PDMC) as a template. The PDMC pores serve as physical barriers during the condensation and pyrolysis of a titania precursor, preventing the titania NPs from growing beyond 10 nm in size. Unlike most titania nanomaterials, during pyrolysis the NPs undergo no transition from the anatase to rutile phase and they become catalytically active reduced TiO_2?x. When exposed to a slow electron beam, the NPs exhibit a charge/discharge behavior, lighting up and fading away for an average period of 15 s for an extended period of time. The NPs also show a 50 nm red‐shift in their UV/Vis absorption and long‐lived charge carriers (electrons and holes) at room temperature in the dark, even long after UV irradiation. The NPs as photocatalysts show a good activity for CO₂ reduction.     

The Stabilization Effect of CO2 in Lithium–Oxygen/CO2 Batteries

The lithium (Li)–air battery has an ultrahigh theoretical specific energy, however, even in pure oxygen (O₂), the vulnerability of conventional organic electrolytes and carbon cathodes towards reaction intermediates, especially O₂^?, and corrosive oxidation and crack/pulverization of Li metal anode lead to poor cycling stability of the Li‐air battery. Even worse, the water and/or CO₂ in air bring parasitic reactions and safety issues. Therefore, applying such systems in open‐air environment is challenging. Herein, contrary to previous assertions, we have found that CO₂ can improve the stability of both anode and electrolyte, and a high‐performance rechargeable Li–O₂/CO₂ battery is developed. The CO₂ not only facilitates the in situ formation of a passivated protective Li₂CO₃ film on the Li anode, but also restrains side reactions involving electrolyte and cathode by capturing O₂^?. Moreover, the Pd/CNT catalyst in the cathode can extend the battery lifespan by effectively tuning the product morphology and catalyzing the decomposition of Li₂CO₃. The Li–O₂/CO₂ battery achieves a full discharge capacity of 6628 mAh g^?1 and a long life of 715 cycles, which is even better than those of pure Li–O₂ batteries.     

Spiro-Carbon: A Metallic Carbon Allotrope Predicted from First Principles Calculations

A structurally stable microporous metallic carbon allotrope, poly(spiro[2.2]penta-1,4-diyne) or, for short, spiro-carbon, with I4₁/amd (D_4h) symmetry is predicted by first-principles calculations using density functional theory (DFT). The calculations of electronic, vibrational, and structural properties show that spiro-carbon has lower relative energy than other elusive carbon allotropes such as T-Carbon and 1-diamondyne (Y-Carbon). Its structure can be pictured as a set of trans-cisoid-polyacetylene chains tangled and interconnected together by sp³ carbon atoms. Calculations reveal a metallic electronic structure arising from an “intrinsic doping” of trans-cisoid-polyacetylene chains with sp³ carbon atoms. Possible synthetic routes and various simulated spectra (XRD, NMR, and IR absorption) are provided in order to guide future efforts to synthesize this novel material.     

Kinetic Isotope Effect as a Tool To Investigate the Oxygen Reduction Reaction on Pt-based Electrocatalysts – Part II: Effect of Platinum Dispersion

We investigated the oxygen reduction reaction (ORR) mechanism on Pt nanoparticles (NPs) dispersed on several carbon blacks with various physicochemical properties (i. e. specific surface ranging from 80 to 900 m² g⁻¹, different graphitization degree, etc.). Using the kinetic isotope effect (KIE) along with various electrochemical characterizations, we determined that the rate determining step (RDS) of the ORR is a proton-independent step when the density of Pt NPs on the surface of the carbon support is high. Upon decrease of the density of Pt NPs on the surface, the RDS of the ORR starts involving a proton, as denoted by an increase of the KIE >1. This underlined the critical role played by the carbon support in the oxygen reduction reaction electrocatalysis by Pt supported on high surface area carbon.