Enantioselective and Band-Gap Modulation in Photocatalysis of Metal-Free Chiral Carbon Dots.

Photodriven chiral catalysis is the combination of photocatalysis and chiral catalysis and is considered one of the cleanest and most efficient methods for the synthesis of chiral compounds or drugs. Furthermore, due to the potential metal contamination associated with most metal-based catalysts, metal-free chiral photocatalysts are ideal candidates. In this work, we demonstrate that metal-free chiral carbon dots (CDs) exhibit size-dependent enantioselective photocatalytic activity. Using serine as the raw material, chiral CDs with well-defined structures and average sizes of 2.22, 3.01, 3.70, 4.77, and 7.21 nm were synthesized using the electrochemical method. These chiral CDs possess size-dependent band gaps and exhibit photoresponsive enantioselective catalytic activity toward the oxidation of dihydroxyphenylalanine (DOPA). Under light-assisted conditions, chiral CDs (L72, 500 µg/mL) exhibit high selectivity (selectivity factor: 2.07) and maintain a certain level of catalytic activity (1.34 µM/min) even at a low temperature of 5 °C. The high catalytic activity of the chiral CDs arises from their photoelectrons reducing O2 to generate O2-, as the active oxygen species for DOPA oxidation. The high enantioselectivity of the chiral CDs is attributed to their differential adsorption capabilities toward DOPA enantiomers. This study provides a new approach for designing metal-free chiral photocatalysts with high enantioselectivity.

Characterization of the complete chloroplast genome of Eutrema deltoideum (Brassicaceae).

Eutrema deltoideum (Hook. f. et Thoms.) has been recognized as a potentially important vegetable and medicinal resource. In this study, we present the complete chloroplast genome of E. deltoideum and conduct a phylogenetic analysis. The chloroplast genome is 154,051 bp long and consists of a large single-copy (LSC) region of 84,149 bp, two inverted repeat (IR) regions of 26,065 bp each, and a small single-copy (SSC) region of 17,772 bp. It contains 132 complete genes, including 87 protein-coding genes, 8 ribosomal RNA genes, and 37 tRNA genes. Additionally, we identified 78 simple sequence repeats (SSRs). The phylogenetic tree reveals that E. deltoideum is closely related to E. heterophyllum, and the Eutrema genus is monophyletic. This study provides valuable information about E. deltoideum and enhances our understanding of its taxonomic classification.

Understanding Advanced Transition Metal-Based Two Electron Oxygen Reduction Electrocatalysts from the Perspective of Phase Engineering.

Non-noble transition metal (TM)-based compounds have recently become a focal point of extensive research interest as electrocatalysts for the two electron oxygen reduction (2e- ORR) process. To efficiently drive this reaction, these TM-based electrocatalysts must bear unique physiochemical properties, which are strongly dependent on their phase structures. Consequently, adopting engineering strategies toward the phase structure has emerged as a cutting-edge scientific pursuit, crucial for achieving high activity, selectivity, and stability in the electrocatalytic process. This comprehensive review addresses the intricate field of phase engineering applied to non-noble TM-based compounds for 2e- ORR. First, the connotation of phase engineering and fundamental concepts related to oxygen reduction kinetics and thermodynamics are succinctly elucidated. Subsequently, the focus shifts to a detailed discussion of various phase engineering approaches, including elemental doping, defect creation, heterostructure construction, coordination tuning, crystalline design, and polymorphic transformation to boost or revive the 2e- ORR performance (selectivity, activity, and stability) of TM-based catalysts, accompanied by an insightful exploration of the phase-performance correlation. Finally, the review proposes fresh perspectives on the current challenges and opportunities in this burgeoning field, together with several critical research directions for the future development of non-noble TM-based electrocatalysts.

Carbon dots derived from metformin by electrochemical synthesis with broad-spectrum antibacterial properties.

Due to the advantages of good aqueous dispersion and biocompatibility, carbon dots (CDs) are promising candidates for a wide range of applications in the biological field. Notably, CDs derived from biosafe organic precursors will contribute both new types of CDs and new bioactivities. Herein, metformin (MET), a first-line drug for the treatment of type II diabetes, was selected as an organic precursor to fabricate a new type of CDs, namely, semi-carbonized MET (MCDs). These MCDs derived from MET possess a completely new antibacterial activity against Staphylococcus aureus (SA) and Escherichia coli (E. coli) compared with that of MET and achieve complete antibacterial activity at 200 µg mL-1. The broad-spectrum antibacterial mechanism of MCDs involves two aspects. For the Gram-positive bacteria SA, MCDs mainly affect the transport of nutrients by adsorbing onto the surface of bacteria, thereby inhibiting bacterial growth. For the Gram-negative bacteria E. coli, MCDs can easily pass through their thin cell walls and stimulate the bacteria to produce excess ROS, eventually leading to the death of the bacteria. This work may open a new way for the future design and development of CDs prepared from biosafe organic precursors with specific functions.

Enhanced the intrinsic oxidase-like activity of chiral carbon dots via manganese doping for selective catalytic oxidation.

It is highly desirable to design and construct chemical catalysts with high activity and specificity as the alternatives of natural enzymes for industrial application. Chiral carbon dots (CDs), possessing both the intrinsic enzyme-like activity and specific recognition ability, are one of good candidates for enzyme-like catalysts. However, their catalytic activity is far from that of natural enzymes and needs to be enhanced. In this work, the modulation of the chiral structure and catalytic activity of chiral CDs with intrinsic oxidase-like activity was implemented by manganese (Mn) doping. Under the light condition, chiral CDs (l-Ser-CDs and d-Ser-CDs) derived from chiral serine (Ser) show weak catalytic activity and low selectivity toward the oxidation of L type of dopamine (l-DOPA), whereas the Mn functionalized chiral CDs (l-Mn-CDs or d-Mn-CDs) exhibit 6.9 times higher in catalytic activity and 2.9 times in selectivity ratio (SR) than Ser-CDs. Mn-CDs involve two-path catalytic process, in which the photogenerated electrons could reduce O2 to O2- as the active species and the holes would oxidize DOPA directly. Moreover, doping of Mn enables the CDs to generate more O2-. Besides, l-Mn-CDs have higher catalytic activity than that of d-Mn-CDs (+54.2 %), and the chiral Mn-CDs have stronger selective adsorption capacity towards chiral DOPA than Ser-CDs. Our work provides a new method for designing and preparing novel chiral artificial enzymes.

Layered Quasi-Nevskite Metastable-Phase Cobalt Oxide Accelerates Alkaline Oxygen Evolution Reaction Kinetics.

Clarifying the structure-reactivity relationship of non-noble-metal electrocatalysts is one of the decisive factors for the practical application of water electrolysis. In this field, the anodic oxygen evolution reaction (OER) with a sluggish kinetic process has become a huge challenge for large-scale production of high-purity hydrogen. Here we synthesize a layered quasi-nevskite metastable-phase cobalt oxide (LQNMP-Co2O3) nanosheet via a simple molten alkali synthesis strategy. The unit-cell parameters of LQNMP-Co2O3 are determined to be a = b = 2.81 Šand c = 6.89 Šwith a space group of P3̅m1 (No. 164). The electrochemical results show that the LQNMP-Co2O3 electrocatalyst enables delivering an ultralow overpotential of 266 mV at a current density of 10 mA cmgeo-2 with excellent durability. The operando XANES and EXAFS analyses clearly reveal the origin of the OER activity and the electrochemical stability of the LQNMP-Co2O3 electrocatalyst. Density functional theory (DFT) simulations show that the energy barrier of the rate-determining step (RDS) (from *O to *OOH) is significantly reduced on the LQNMP-Co2O3 electrocatalyst by comparing with simulated monolayered CoO2 (M-CoO2).

Light-Induced Variation of Lithium Coordination Environment in g-C3N4 Nanosheet for Highly Efficient Oxygen Reduction Reactions.

The structure and electronic state of the active center in a single-atom catalyst undergo noticeable changes during a dynamic catalytic process. The metal atom active center is not well demonstrated in a dynamic manner. This study demonstrated that Li metal atoms, serving as active centers, can migrate on a C3N4 monolayer or between C3N4 monolayers when exposed to light irradiation. This migration alters the local coordination environment of Li in the C3N4 nanosheets, leading to a significant enhancement in photocatalytic activity. The photocatalytic H2O2 process could be maintained for 35 h with a 920 mmol/g record-high yield, corresponding to a 0.4% H2O2 concentration, which is far greater than the value (0.1%) of practical application for wastewater treatment. Density functional theory calculations indicated that dynamic Li-coordinated structures contributed to the superhigh photocatalytic activity.

In Situ Insertion of Silicon Nanowires into Hollow Porous Co/NC Polyhedra Enabling Large-Current-Density Hydrogen Evolution Electrocatalysis.

N-doped carbon (NC)-encapsulated transition metal (TM) nanocomposites are considered as alternatives to Pt-based hydrogen evolution reaction (HER) electrocatalysts; however, their poor electron transfer and mass diffusion capability at high current densities hinder their practical application. Herein, an oriented coupling strategy for the in situ grafting of ultrafine Co nanoparticle-embedded hollow porous C polyhedra onto Si nanowires (Co/NC-HP@Si-NWs) is proposed to address this concern. Experimental investigations reveal that the intimate coupling between the Si-NW and Co/NC nanocage forms a multithreaded conductive network, lowering the energy barrier for internal electron transfer. When functionalized as an HER electrocatalyst in 0.5 m H2 SO4 , Co/NC-HP@Si-NWs deliver overpotentials as low as 57 and 440 mV at 10 and 500 mA cm-2 , respectively, which are much better than those of the pristine Co/NC-HP. Moreover, Co/NC-HP@Si-NWs show an outstanding cycle durability of 24 h at 10 and 500 mA cm-2 . The findings of this study are expected to inspire revolutionary work on the development of Si-mediated TM-based electrocatalysts for the HER.

Emergent Intrinsic Ferromagnetism in Two-Dimensional Trigonal Rhodium Oxide.

Two-dimensional (2D) van der Waals single crystals with long-range magnetic order are the precondition and urgent task for developing a 2D spintronics device. In contrast to graphene and transition metal dichalcogenides, the study of 2D single-crystal metal oxides with intrinsic ferromagnetic properties remains a huge challenge. Here, we report a large-size trigonal single-crystal rhodium oxide (SC-Tri-RhO2), with crystal parameters of a = b = 3.074 Å, c = 6.116 Å, and a space group of P3̅m1 (164), exhibiting strong ferromagnetism (FM) at a rather high temperature. Furthermore, theoretical calculations suggest that the ferromagnetism in SC-Tri-RhO2 originates from spin splitting near the Fermi level, and the total magnetic moment is contributed mainly by the Rh atom.

C3N nanodots inhibits Aß peptides aggregation pathogenic path in Alzheimer's disease.

Despite the accumulating evidence linking the development of Alzheimer's disease (AD) to the aggregation of Aß peptides and the emergence of Aß oligomers, the FDA has approved very few anti-aggregation-based therapies over the past several decades. Here, we report the discovery of an Aß peptide aggregation inhibitor: an ultra-small nanodot called C3N. C3N nanodots alleviate aggregation-induced neuron cytotoxicity, rescue neuronal death, and prevent neurite damage in vitro. Importantly, they reduce the global cerebral Aß peptides levels, particularly in fibrillar amyloid plaques, and restore synaptic loss in AD mice. Consequently, these C3N nanodots significantly ameliorate behavioral deficits of APP/PS1 double transgenic male AD mice. Moreover, analysis of critical tissues (e.g., heart, liver, spleen, lung, and kidney) display no obvious pathological damage, suggesting C3N nanodots are biologically safe. Finally, molecular dynamics simulations also reveal the inhibitory mechanisms of C3N nanodots in Aß peptides aggregation and its potential application against AD.

Stable and oxidative charged Ru enhance the acidic oxygen evolution reaction activity in two-dimensional ruthenium-iridium oxide.

The oxygen evolution reactions in acid play an important role in multiple energy storage devices. The practical promising Ru-Ir based catalysts need both the stable high oxidation state of the Ru centers and the high stability of these Ru species. Here, we report stable and oxidative charged Ru in two-dimensional ruthenium-iridium oxide enhances the activity. The Ru0.5Ir0.5O2 catalyst shows high activity in acid with a low overpotential of 151 mV at 10 mA cm-2, a high turnover frequency of 6.84 s-1 at 1.44 V versus reversible hydrogen electrode and good stability (618.3 h operation). Ru0.5Ir0.5O2 catalysts can form more Ru active sites with high oxidation states at lower applied voltages after Ir incorporation, which is confirmed by the pulse voltage induced current method. Also, The X-ray absorption spectroscopy data shows that the Ru-O-Ir local structure in two-dimensional Ru0.5Ir0.5O2 solid solution improved the stability of these Ru centers.

Microwave Regenerable Nickel, Zinc Co-doped Nitrogen-Coordinated Porous Carbon Catalyst for Nitrogen Fixation.

More than 90% of the global NH3 synthesis is dominated by the Haber-Bosch process, which consumes 2% of the worldwide energy and generates 1.44% of the global carbon emission. The electrochemical N2 reduction reaction (NRR) is regarded as an attractive alternative route to produce NH3 under mild reaction conditions, but the electrocatalysts suffer from the difficulty of N≡N cleavage. In this work, we report a leaf-like MOF-derived Ni/Zn bimetallic co-doped nitrogen-coordinated porous carbon (Ni/Zn-NPC) as a cost-effective NH3 synthesis electrocatalyst. The resultant electrocatalyst achieved a high NH3 production rate of 22.68 µg h-1 mgcat-1 at -1.0 V vs a reversible hydrogen electrode (RHE) in a 0.1 M Na2SO4 electrolyte. The Ni/Zn-NPC material can be called a microwave regenerable catalyst because microwave treatment has proven to be a crucial part of the multi-field coupling to detoxify and make the catalyst reactive, further improving its stability. Density functional theory (DFT) was chosen to explore the mechanism of Ni/Zn-NPC for NRR, providing a profound prediction of the structure of the active site and related reaction pathways and revealing that trace Ni doping optimizes the local coordination environment and N2 adsorption of Zn atoms.

Electron delocalization of robust high-nuclear bismuth-oxo clusters for promoted CO2 electroreduction.

The integration of high activity, selectivity and stability in one electrocatalyst is highly desirable for electrochemical CO2 reduction (ECR), yet it is still a knotty issue. The unique electronic properties of high-nuclear clusters may bring about extraordinary catalytic performance; however, construction of a high-nuclear structure for ECR remains a challenging task. In this work, a family of calix[8]arene-protected bismuth-oxo clusters (BiOCs), including Bi4 (BiOC-1/2), Bi8Al (BiOC-3), Bi20 (BiOC-4), Bi24 (BiOC-5) and Bi40Mo2 (BiOC-6), were prepared and used as robust and efficient ECR catalysts. The Bi40Mo2 cluster in BiOC-6 is the largest metal-oxo cluster encapsulated by calix[8]arenes. As an electrocatalyst, BiOC-5 exhibited outstanding electrochemical stability and 97% Faraday efficiency for formate production at a low potential of -0.95 V vs. RHE, together with a high turnover frequency of up to 405.7 h-1. Theoretical calculations reveal that large-scale electron delocalization of BiOCs is achieved, which promotes structural stability and effectively decreases the energy barrier of rate-determining *OCHO generation. This work provides a new perspective for the design of stable high-nuclear clusters for efficient electrocatalytic CO2 conversion.

Green carbon dots derived from Atractylodes macrocephala: A potential nanodrug for treating alcoholic gastric ulcer.

Alcoholic gastric ulcer is a common acute gastric injury disease. The drugs currently used in clinical practice not only cannot fundamentally treat gastric injury, but also have serious side effects. There is an urgent demand for the discovery of a mild drug to treat alcoholic gastric ulcers. Herein, the green carbon dots derived from charred Atractylodes macrocephala (CAM-CDs) were acquired and have been proven to be safe and effective in alleviating alcoholic gastric ulcers at an inhibition rate up to 60%. CAM-CDs can markedly attenuate the gastric mucosa damage such as mucosal defect, bleeding and inflammatory cell infiltration by histopathological examination. Serum and tissue inflammatory cytokine measurements, as well as immunohistochemistry results, indicate that its mechanism of gastric mucosal protection may involve the reduction of IL-1ß and TNF-α by regulating inflammatory signaling pathway of the NF-κB/NLRP3 axis, as well as elevation of IL-10 levels. CAM-CDs also can reduce oxidative stress markers (MDA), increase PGE2 and mucin secretion (MUC5AC), and it simultaneously exerts slight inhibition of hydrogen potassium ATPase and pepsin activity to protect gastric mucosa, as well as increases the microbial diversity and regulates species composition of gut microbiota in rats with gastric ulcer. Our work provides a new perspective on utilizing carbon-based nanomaterials in the development of new mild drugs.

Oxygen Vacancy Engineering of Fe-Doped NiMoO4 for Electrocatalytic N2 Fixation to NH3.

Electrochemical nitrogen reduction reaction (NRR) is a promising method for ammonia synthesis under ambient conditions. However, the NRR performance is limited to an extremely strong N≡N bond in N2 and the competing hydrogen evolution reaction. Introducing oxygen vacancies (OVs) has been considered as a forceful means to accelerate the sluggish NRR reaction kinetics. Herein, we reported the design of Fe-doped NiMoO4 catalysts for NRR. Fe doping can increase the amount of OVs in the catalyst and contribute to lattice strain enhancement, thereby leading to the improvement of the electron transport rate and catalytic active for NRR. In 0.1 M Na2SO4 solution, the 5% Fe-NiMoO4 catalyst achieves a NH3 yield rate of 15.36 µg h-1 mgcat.-1 and a Faradaic efficiency of 26.85% under -0.5 V versus RHE. Furthermore, the 5% Fe-NiMoO4 catalyst exhibits excellent stability (up to 13 h) during the reaction.

Immobilization of Oxyanions on the Reconstructed Heterostructure Evolved from a Bimetallic Oxysulfide for the Promotion of Oxygen Evolution Reaction.

Efficient and durable oxygen evolution reaction (OER) requires the electrocatalyst to bear abundant active sites, optimized electronic structure as well as robust component and mechanical stability. Herein, a bimetallic lanthanum-nickel oxysulfide with rich oxygen vacancies based on the La2O2S prototype is fabricated as a binder-free precatalyst for alkaline OER. The combination of advanced in situ and ex situ characterizations with theoretical calculation uncovers the synergistic effect among La, Ni, O, and S species during OER, which assures the adsorption and stabilization of the oxyanion [Formula: see text] onto the surface of the deeply reconstructed porous heterostructure composed of confining NiOOH nanodomains by La(OH)3 barrier. Such coupling, confinement, porosity and immobilization enable notable improvement in active site accessibility, phase stability, mass diffusion capability and the intrinsic Gibbs free energy of oxygen-containing intermediates. The optimized electrocatalyst delivers exceptional alkaline OER activity and durability, outperforming most of the Ni-based benchmark OER electrocatalysts.

The Key Effect of Carboxyl Group and CuN2 O2 Coordinate Structure for Cu, N Co-Doped Carbon Dots with Peroxidase-Like Property.

Carbon dots (CDs) with good water solubility and biocompatibility have become a research hotspot in the nano-enzyme and biomedical field. However, the problems of low catalytic activity and ambiguous catalytic site of CDs as nanozymes still need to be addressed. In this work, CDs loaded with Cu single atoms are obtained through pyrolysis, and the coordination structure and surface functional groups are regulated by adjusting the pyrolysis temperature. CDs obtained at 300 °C (named Cu-CDs-300) have the most carboxyl content and Cu is coordinated in the form of CuN2 O2 , which can better decompose H2 O2 to produce free radical and is beneficial to catalyze the oxidation of 3,3',5,5'-tetramethylbenzidine (TMB). The vmax is 6.56*10-7  m s-1 , 6.56 times higher than that of horseradish peroxidase (HRP). Moreover, Cu-CDs-300 can effectively lead to CT26 apoptosis by generating much free radicals. This work demonstrates the synergistic effect of oxygen-containing functional groups and metal coordination structures on peroxide-like activity of CDs and provides new ideas for the design of clear active structure and high efficiency peroxide-like single atom CDs catalyst.

Iridium oxide nanoribbons with metastable monoclinic phase for highly efficient electrocatalytic oxygen evolution.

Metastable metal oxides with ribbon morphologies have promising applications for energy conversion catalysis, however they are largely restricted by their limited synthesis methods. In this study, a monoclinic phase iridium oxide nanoribbon with a space group of C2/m is successfully obtained, which is distinct from rutile iridium oxide with a stable tetragonal phase (P42/mnm). A molten-alkali mechanochemical method provides a unique strategy for achieving this layered nanoribbon structure via a conversion from a monoclinic phase K0.25IrO2 (I2/m (12)) precursor. The formation mechanism of IrO2 nanoribbon is clearly revealed, with its further conversion to IrO2 nanosheet with a trigonal phase. When applied as an electrocatalyst for the oxygen evolution reaction in acidic condition, the intrinsic catalytic activity of IrO2 nanoribbon is higher than that of tetragonal phase IrO2 due to the low d band centre of Ir in this special monoclinic phase structure, as confirmed by density functional theory calculations.

Conventional and Inverted Light-Emitting Diodes with 386 nm Emission Wavelength Based on Metal-Free Carbon Dots.

Ultraviolet (UV) light-emitting diodes (LEDs) are of great concern due to wide applications in the fields of solid-state displays, photocommunication, and scientific and medical instruments. During the past 10 years, organic and inorganic semiconductors have made great breakthroughs in short-wavelength emission. Nowadays, carbon dots (CDs), which possess distinctive superiorities of high stability, nontoxicity, and low cost, are promising all-band emission materials for the next generation of LEDs. However, the fabrication of CD-based LEDs (CD-LEDs) with emission wavelengths below 400 nm is still a huge limitation in this field. Herein, we prepared UV emission CDs with the photoluminescence emission wavelength of 371 nm. The UV-CDs are perfectly compatible with both conventional and inverted device structures so as to realize the currently shortest electroluminescent emission wavelength of 386 nm for CD-LEDs. The conventional UV-CD-LEDs possess the optimum luminance of 268 cd m-2 (5427 W sr-1 m-2) with an external quantum efficiency (EQE) of 1.115%. Meanwhile, the inverted UV-CD-LEDs possess the optimum luminance of 132 cd m-2 (2673 W sr-1 m-2) with an EQE of 0.869%. This work paves a new road to manufacture carbon nanomaterial-based UV emission devices with high luminance, EQE, and stability.