The Key Effect of Carboxyl Group and CuN2O2 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 CuN₂O₂, which can better decompose H₂O₂ to produce free radical and is beneficial to catalyze the oxidation of 3,3′,5,5′-tetramethylbenzidine (TMB). The v_max 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.     

基于HS-SPME-GC-MS与电子舌分析冷藏冠玉枇杷的风味特性

目的 探讨冷藏对枇杷果实风味品质的影响。方法 采用顶空固相微萃取-气相色谱质谱联用(HS-SPME/GC-MS)、液相色谱和电子舌检测技术,研究冠玉枇杷在温度为(6±0.5)℃,相对湿度为90%~95%的环境下果实的滋味特性、酸度、糖组分含量及挥发性物质的变化情况。结果 电子舌检测结果表明,在贮藏过程中枇杷的酸味下降明显,贮藏14 d后味觉指标发生显著变化,主成分1的方差贡献率达到85.17%,酸味、甜味与可溶性固形物、pH值呈高度相关性,与可溶性糖缺乏关联性。蔗糖含量在冷藏过程中表现为持续下降趋势,质量损失率为56.7%。HS-SPME/GC-MS结果表明,在枇杷果实中共检测出37种挥发性物质,其中醛类化合物为枇杷的主要挥发性成分,相对含量接近40%。挥发性物质的种类和含量随着贮藏时间会发生变化,己醛的相对含量会降低,(E)-2-己醛含量显著增加。结论 在冷藏过程中,冠玉枇杷果实的酸味明显下降,蔗糖含量显著减少,主要香气成分己醛和(E)-2-己醛可以作为枇杷采后贮藏品质评价的重要指标,并且在贮藏14~21 d期间是风味变化较为明显的阶段。     

Heterogeneous Single‐Atom Catalyst for Visible‐Light‐Driven High‐Turnover CO2 Reduction: The Role of Electron Transfer

Visible‐light‐driven conversion of CO₂ into chemical fuels is an intriguing approach to address the energy and environmental challenges. In principle, light harvesting and catalytic reactions can be both optimized by combining the merits of homogeneous and heterogeneous photocatalysts; however, the efficiency of charge transfer between light absorbers and catalytic sites is often too low to limit the overall photocatalytic performance. In this communication, it is reported that the single‐atom Co sites coordinated on the partially oxidized graphene nanosheets can serve as a highly active and durable heterogeneous catalyst for CO₂ conversion, wherein the graphene bridges homogeneous light absorbers with single‐atom catalytic sites for the efficient transfer of photoexcited electrons. As a result, the turnover number for CO production reaches a high value of 678 with an unprecedented turnover frequency of 3.77 min^?1, superior to those obtained with the state‐of‐the‐art heterogeneous photocatalysts. This work provides fresh insights into the design of catalytic sites toward photocatalytic CO₂ conversion from the angle of single‐atom catalysis and highlights the role of charge kinetics in bridging the gap between heterogeneous and homogeneous photocatalysts.     

Improving the Catalytic Activity of Carbon‐Supported Single Atom Catalysts by Polynary Metal or Heteroatom Doping

Single atom catalysts (SACs) are widely researched in various chemical transformations due to the high atomic utilization and catalytic activity. Carbon‐supported SACs are the largest class because of the many excellent properties of carbon derivatives. The single metal atoms are usually immobilized by doped N atoms and in some cases by C geometrical defects on carbon materials. To explore the catalytic mechanisms and improve the catalytic performance, many efforts have been devoted to modulating the electronic structure of metal single atomic sites. Doping with polynary metals and heteroatoms has been recently proposed to be a simple and effective strategy, derived from the modulating mechanisms of metal alloy structure for metal catalysts and from the donating/withdrawing heteroatom doping for carbon supports, respectively. Polynary metals SACs involve two types of metal with atomical dispersion. The bimetal atom pairs act as dual catalytic sites leading to higher catalytic activity and selectivity. Polynary heteroatoms generally have two types of heteroatoms in which N always couples with another heteroatom, including B, S, P, etc. In this Review, the recent progress of polynary metals and heteroatoms SACs is summarized. Finally, the barriers to tune the activity/selectivity of SACs are discussed and further perspectives presented.     

Regulating Electronic Structure of Iron Nitride by Tungsten Nitride Nanosheets for Accelerated Overall Water Splitting

Two essential characteristics that are required for hybrid electrocatalysts to exhibit higher oxygen and hydrogen evolution reaction (OER and HER, respectively) activity are a favorable electronic configuration and a sufficient density of active sites at the interface between the two materials within the hybrid. In the present study, a hybrid electrocatalyst is introduced with a novel architecture consisting of coral-like iron nitride (Fe₂N) arrays and tungsten nitride (W₂N₃) nanosheets that satisfies these requirements. The resulting W₂N₃/Fe₂N catalyst achieves high OER activity (268.5 mV at 50 mA cm⁻²) and HER activity (85.2 mV at 10 mA cm⁻²) with excellent long-term durability in an alkaline medium. In addition, density functional theory calculations reveal that the individual band centers experience an upshift in the hybrid W₂N₃/Fe₂N structure, thus improving the OER and HER activity. The strategy adopted here thus provides a valuable guide for the fabrication of cost-effective multi-metallic crystalline hybrids for use as multifunctional electrocatalysts.     

Electronic Modulation of Metal-Organic Frameworks Caused by Atomically Dispersed Ru for Efficient Hydrogen Evolution

Designing excellent electrocatalysts for the hydrogen evolution reaction (HER) is extremely significant in producing clean and sustainable hydrogen fuel. Herein, a rational strategy is developed to fabricate a promising electrocatalyst by introducing atomically dispersed Ru into a cobalt-based metal-organic framework (MOF), Co-BPDC (Co(bpdc)(H₂O)₂, BPDC: 4,4'-Biphenyldicarboxylic acid). The obtained CoRu-BPDC nanosheet arrays exhibit remarkable HER performance with an overpotential of 37 mV at a current density of 10 mA cm⁻² in alkaline media, which is superior to most of the MOF-based electrocatalysts and comparable to the commercial Pt/C. Synchrotron radiation-based X-ray absorption fine structure (XAFS) spectroscopy studies verify that the isolated Ru atoms are dispersed in Co-BPDC nanosheets with the formation of five-coordinated Ru-O₅ species. XAFS spectroscopy combined with density functional theory (DFT) calculations unravels that atomically dispersed Ru can modulate the electronic structure of the as-obtained Co-BPDC, contributing to the optimization of binding strength for H* and the enhancement of HER performance. This work opens a new avenue to rationally design highly-active single-atom modified MOF-based HER electrocatalysts via modulating electronic structures of MOF.     

Asymmetric Active Sites for Boosting Oxygen Evolution Reaction

Transition metal-nitrogen-carbon materials with atomically dispersed active sites are promising catalysts for oxygen evolution reaction (OER) since they combine the strengths of both homogeneous and heterogeneous catalysts. However, the canonically symmetric active site usually exhibits poor OER intrinsic activity due to its excessively strong or weak oxygen species adsorption. Here, a catalyst with asymmetric MN₄ sites based on the 3-s-triazine of g-C₃N₄ (termed as a-MN₄@NC) is proposed. Compared to symmetric, the asymmetric active sites directly modulate the oxygen species adsorption via unifying planar and axial orbitals (dx²-y², dz²), thus enabling higher OER intrinsic activity. In Silico screening suggested that cobalt has the best OER activity among familiar nonprecious transition metal. These experimental results suggest that the intrinsic activity of asymmetric active sites (179 mV overpotential at onset potential) is enhanced by 48.4% compared to symmetric under similar conditions. Remarkably, a-CoN₄@NC showed excellent activity in alkaline water electrolyzer (AWE) device as OER catalyst, the electrolyzer only required 1.7 V and 2.1 V respectively to reach the current density of 150 mA cm⁻² and 500 mA cm⁻². This work opens an avenue for modulating the active sites to obtain high intrinsic electrocatalytic performance including, but not limited to, OER.     

Zinc-Mediated Template Synthesis of Fe-N-C Electrocatalysts with Densely Accessible Fe-Nx Active Sites for Efficient Oxygen Reduction

Owing to their earth abundance, high atom utilization, and excellent activity, single iron atoms dispersed on nitrogen-doped carbons (Fe-N-C) have emerged as appealing alternatives to noble-metal platinum (Pt) for catalyzing the oxygen reduction reaction (ORR). However, the ORR activity of current Fe-N-C is seriously limited by the low density and inferior exposure of active Fe-N_x species. Here, a novel zinc-mediated template synthesis strategy is demonstrated for constructing densely exposed Fe-N_x moieties on hierarchically porous carbon (SA-Fe-NHPC). During the thermal treatment of 2,6-diaminopyridine/ZnFe/SiO₂ complex, the zinc prevents the formation of iron carbide nanoparticles and the SiO₂ template promotes the generation of hierarchically pores for substantially improving the accessibility of Fe-N_x moieties after subsequent leaching. As a result, the SA-Fe-NHPC electrocatalysts exhibit an unprecedentedly high ORR activity with a half-wave potential (E_1/2) of 0.93 V in a 0.1 m KOH aqueous solution, which outperforms those for Pt/C catalyst and state-of-the-art noble metal-free electrocatalysts. As the air electrode in zinc–air batteries, the SA-Fe-NHPC demonstrates a large peak power density of 266.4 mW cm⁻² and superior long-term stability. Therefore, the developed zinc-mediated template synthesis strategy for boosting the density and accessibility of Fe-N_x species paves a new avenue toward high-performance ORR electrocatalysts.     

Adjusting the Structure and Electronic Properties of Carbons for Metal‐Free Carbocatalysis of Organic Transformations

Carbon nanomaterials doped with some other lightweight elements were recently described as powerful, heterogeneous, metal‐free organocatalysts, adding to their high performance in electrocatalysis. Here, recent observations in traditional catalysis are reviewed, and the underlying reaction mechanisms of the catalyzed organic transformations are explored. In some cases, these are due to specific active functional sites, but more generally the catalytic activity relates to collective properties of the conjugated nanocarbon frameworks and the electron transfer from and to the catalytic centers and substrates. It is shown that the learnings are tightly related to those of electrocatalysis; i.e., the search for better electrocatalysts also improves chemocatalysis, and vice versa. Carbon–carbon heterojunction effects and some perspectives on future possibilities are discussed at the end.     

Dual Active Sites of Oversaturated Fe-N5 and Fe2O3 Nanoparticles for Accelerating Redox Kinetics of Polysulfides

The shuttling effect and sluggish reaction kinetics are the main bottlenecks for the commercial viability of lithium–sulfur (Li–S) batteries. Metal-nitrogen-carbon single atom catalysts have attracted much attention to overcoming these obstacles due to their novel electrocatalytic activity. Herein, a novel cooperative catalytic interface with dual active sites (oversaturated Fe-N₅ and polar Fe₂O₃ nanocrystals) are co-embedded in nitrogen-doped hollow carbon spheres (Fe₂O₃/Fe-SA@NC) is designed by fine atomic regulation mechanism. Both experimental verifications and theoretical calculations disclose that the dual active sites (Fe-N₅ and Fe₂O₃) in this catalyst (Fe₂O₃/Fe-SA@NC) tend to form “Fe S” and “Li N/O” bond, synchronically enhancing chemical adsorption and interface conversion ability of polysulfides, respectively. Specially, the Fe-N₅ coordination with 3D configuration and sulfiphilic superfine Fe₂O₃ nanocrystals exhibit the strong adsorption ability to facilitate the subsequent conversion reaction at dual-sites. Meanwhile, the nitrogen-doped hollow carbon spheres can promote Li⁺/electron transfer and physically suppress polysulfides shuttling. Consequently, Li–S battery with the Fe₂O₃/Fe-SA@NC-modified separator exhibits a high capacity retention of 78% after 800 cycles at 1 C (pure S cathode, S content: 70 wt.%). Furthermore, the pouch cell with this separator shows good performance at 0.1 C for practical application (S loading: 4 mg cm⁻²).