An Unlocked Two-Dimensional Conductive Zn-MOF on Polymeric Carbon Nitride for Photocatalytic H2O2 Production

Developing highly efficient catalytic sites for O₂ reduction to H₂O₂, while ensuring the fast injection of energetic electrons into these sites, is crucial for artificial H₂O₂ photosynthesis but remains challenging. Herein, we report a strongly coupled hybrid photocatalyst comprising polymeric carbon nitride (CN) and a two-dimensional conductive Zn-containing metal–organic framework (Zn-MOF) (denoted as CN/Zn-MOF(lc)/400; lc, low crystallinity; 400, annealing temperature in °C), in which the catalytic capability of Zn-MOF(lc) for H₂O₂ production is unlocked by the annealing-induced effects. As revealed by experimental and theoretical calculation results, the Zn sites coordinated to four O (Zn-O₄) in Zn-MOF(lc) are thermally activated to a relatively electron-rich state due to the annealing-induced local structure shrinkage, which favors the formation of a key *OOH intermediate of 2e⁻ O₂ reduction on these sites. Moreover, the annealing treatment facilitates the photoelectron migration from the CN photocatalyst to the Zn-MOF(lc) catalytic unit. As a result, the optimized catalyst exhibits dramatically enhanced H₂O₂ production activity and excellent stability under visible light irradiation.     

Tuning Local Coordination Environments of Manganese Single-Atom Nanozymes with Multi-Enzyme Properties for Selective Colorimetric Biosensing

Single-atom nanozymes (SAzymes) are promising in next-generation nanozymes, nevertheless, how to rationally modulate the microenvironment of SAzymes with controllable multi-enzyme properties is still challenging. Herein, we systematically investigate the relationship between atomic configuration and multi-enzymatic performances. The constructed Mn_SA−N₃-coordinated SAzymes (Mn_SA−N₃−C) exhibits much more remarkable oxidase-, peroxidase-, and glutathione oxidase-like activities than that of Mn_SA−N₄−C. Based on experimental and theoretical results, these multi-enzyme-like behaviors are highly dependent on the coordination number of single atomic Mn sites by local charge polarization. As a consequence, a series of colorimetric biosensing platforms based on Mn_SA−N₃−C SAzymes is successfully built for specific recognition of biological molecules. These findings provide atomic-level insight into the microenvironment of nanozymes, promoting rational design of other demanding biocatalysts.     

p-Block Bismuth Nanoclusters Sites Activated by Atomically Dispersed Bismuth for Tandem Boosting Electrocatalytic Hydrogen Peroxide Production

Constructing electrocatalysts with p-block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p-block-element bismuth-based (Bi-based) catalyst with the co-existence of single-atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Bi_clu) (collectively denoted as BiOS_SA/Bi_clu) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H₂O₂). As a result, BiOS_SA/Bi_clu gives a high H₂O₂ selectivity of 95 % in rotating ring-disk electrode, and a large current density of 36 mA cm⁻² at 0.15 V vs. RHE, a considerable H₂O₂ yield of 11.5 mg cm⁻² h⁻¹ with high H₂O₂ Faraday efficiency of ∼90 % at 0.3 V vs. RHE and a long-term durability of ∼22 h in H-cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOS_SA/Bi_clu, the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p-block-element Bi catalysts featuring atomic-level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p-block metals.     

Unraveling the Structure Transition and Peroxidase Mimic Activity of Copper Sites over Atomically Dispersed Copper-Doped Carbonized Polymer Dots

The lack of systematic structural resolution makes it difficult to build specific transition-metal-atom-doped carbonized polymer dots (TMA-doped CPDs). Herein, the structure-activity relationship between Cu atoms and CPDs was evaluated by studying the peroxidase-like properties of Glu−Cu−CPDs prepared by using copper glutamate (Glu) with a Cu−N₂O₂ initial structure. The results showed that the Cu atoms bound to Glu−Cu−CPDs in the form of Cu−N₂C₂, indicating that Cu−O bonds changed into Cu−C bonds under hydrothermal conditions. This phenomenon was also observed in other copper-doped CPDs. Moreover, the carboxyl and amino groups content decreased after copper-atom doping. Theoretical calculations revealed a dual-site catalytic mechanism for catalyzing H₂O₂. The detection of intracellular H₂O₂ suggested their application prospects. Our study provides an in-depth understanding of the formation and catalytic mechanism of TMA-doped-CPDs, allowing for the generation specific TMA-doped-CPDs.     

Pauling-Type Adsorption of O2 Induced by Heteroatom Doped ZnIn2S4 for Boosted Solar-Driven H2O2 Production

Breaking the trade-off between activity and selectivity has perennially been a formidable endeavor in the field of hydrogen peroxide (H₂O₂) photosynthesis, especially the side-on configuration of oxygen (O₂) on the catalyst surface will cause the cleavage of O−O bonds, which drastically hinders the H₂O₂ production performance. Herein, we present an atomically heteroatom P doped ZnIn₂S₄ catalyst with tunable oxygen adsorption configuration to accelerate the ORR kinetics essential for solar-driven H₂O₂ production. Indeed, the spectroscopy characterizations (such as EXAFS and in situ FTIR) and DFT calculations reveal that heteroatom P doped ZnIn₂S₄ at substitutional and interstitial sites, which not only optimizes the coordination environment of Zn active sites, but also facilitates electron transfer to the Zn sites and improves charge density, avoiding the breakage of O−O bonds and reducing the energy barriers to H₂O₂ production. As a result, the oxygen adsorption configuration is regulated from side-on (Yeager-type) to end-on (Pauling-type), resulting in the accelerated ORR kinetics from 874.94 to 2107.66 μmol g⁻¹ h⁻¹. This finding offers a new avenue toward strategic tailoring oxygen adsorption configuration by the rational design of doped photocatalyst.     

H_2O_2氧化N_2生成N_2O和H_2O机理的研究

采用量子化学计算方法研究了Ｈ２Ｏ２ 氧化Ｎ２ 生成Ｎ２Ｏ 和Ｈ２Ｏ 的机理．结果发现, Ｈ２Ｏ２ 氧化Ｎ２ 先通过１ 个四元环过渡态形成中间体Ｈ２Ｎ２Ｏ２ 分子,Ｈ２Ｎ２Ｏ２ 再通过一个五元环过渡态形成Ｎ２Ｏ和Ｈ２Ｏ．根据计算得到的每步反应的活化能,得知Ｈ２Ｏ２ 氧化Ｎ２ 生成中间体Ｈ２Ｎ２Ｏ２ 分子是整个反应的控制步骤．     

普鲁士蓝/氧化锆复合材料的电化学行为及对H2O2的电催化

通过一步电沉积技术制备了普鲁士蓝/氧化锆修饰玻碳电极。采用电化学阻抗技术表征修饰电极。采用循环伏安法研究了pH值和扫描速率对该修饰电极的电化学行为的影响。结果表明:普鲁士蓝的峰电流与其扫描速率的一次方在一定范围内呈良好的线性关系。此外,该修饰电极在含有KCl(1.0mol/L)的磷酸盐缓冲溶液(0.1mol/L,pH=7.0)中,对H2O2具有明显的电催化作用,在无酶检测H2O2领域具有潜在的应用价值。     

An Electrochemical Nanosensor for Monitoring the Dynamics of Intracellular H2O2 Upon NADH Treatment

Reactive oxygen species (ROS)-based therapeutic strategies play an important role in cancer treatment. However, in situ, real-time and quantitative analysis of intracellular ROS in cancer treatment for drug screening is still a challenge. Herein we report one selective hydrogen peroxide (H₂O₂) electrochemical nanosensor, which is prepared by electrodeposition of Prussian blue (PB) and polyethylenedioxythiophene (PEDOT) onto carbon fiber nanoelectrode. With the nanosensor, we find that the level of intracellular H₂O₂ increases with NADH treatment and that increase is dose-dependent to the concentration of NADH. High-dose of NADH (above 10 mM) can induce cell death and intratumoral injection of NADH is validated for inhibiting tumor growth in mice. This study highlights the potential of electrochemical nanosensor for tracking and understanding the role of H₂O₂ in screening new anticancer drug.     

Promoting Piezocatalytic H2O2 Production in Pure Water by Loading Metal-Organic Cage-Modified Gold Nanoparticles on Graphitic Carbon Nitride

Piezocatalytic hydrogen peroxide (H₂O₂) production is a green synthesis method, but the rapid complexation of charge carriers in piezocatalysts and the difficulty of adsorbing substrates limit its performance. Here, metal-organic cage-coated gold nanoparticles are anchored on graphitic carbon nitride (MOC-AuNP/g-C₃N₄) via hydrogen bond to serve as the multifunctional sites for efficient H₂O₂ production. Experiments and theoretical calculations prove that MOC-AuNP/g-C₃N₄ simultaneously optimize three key parts of piezocatalytic H₂O₂ production: i) the MOC component enhances substrate (O₂) and product (H₂O₂) adsorption via host–guest interaction and hinders the rapid decomposition of H₂O₂ on MOC-AuNP/g-C₃N₄, ii) the AuNP component affords a strong interfacial electric field that significantly promotes the migration of electrons from g-C₃N₄ for O₂ reduction reaction (ORR), iii) holes are used for H₂O oxidation reaction (WOR) to produce O₂ and H⁺ to further promote ORR. Thus, MOC-AuNP/g-C₃N₄ can be used as an efficient piezocatalyst to generate H₂O₂ at rates up to 120.21 μmol g⁻¹ h⁻¹ in air and pure water without using sacrificial agents. This work proposes a new strategy for efficient piezocatalytic H₂O₂ synthesis by constructing multiple active sites in semiconductor catalysts via hydrogen bonding, by enhancing substrate adsorption, rapid separation of electron-hole pairs and preventing rapid decomposition of H₂O₂.     

Solar Light Driven H2O2 Production and Selective Oxidations Using a Covalent Organic Framework Photocatalyst Prepared by a Multicomponent Reaction

A chemically stable 2D microporous COF ( PMCR-1 ) was synthesized via the multicomponent Povarov reaction. PMCR-1 exhibits a remarkable and long-term stable photocatalytic H₂O₂ production rate (60 h) from pure and sea water under visible light. The H₂O₂ production is markedly enhanced when benzyl alcohol (BA) is added as reductant, which is also due to a strong π–π interaction of BA with dangling phenyl moieties in the COF pores introduced by the multicomponent Povarov reaction. Motivated by the concomitant BA oxidation to benzaldehyde during H₂O₂ formation, the photocatalytic oxidation of various organic substrates such as benzyl amine and methyl sulfide derivatives was investigated. It is shown that the well-defined micropores of PMCR-1 enable size-selective photocatalytic oxidation.     

Cyclodextrin-supported Co(OH)2 Clusters as Electrocatalysts for Efficient and Selective H2O2 Synthesis

Co-based material catalysts have shown attractive application prospects in the 2 e⁻ oxygen reduction reaction (ORR). However, for the industrial synthesis of H₂O₂, there is still lack of Co-based catalysts with high production yield rate. Here, novel cyclodextrin-supported Co(OH)₂ cluster catalysts were prepared via a mild and facile method. The catalyst exhibited remarkable H₂O₂ selectivity (94.2 % ~ 98.2 %), good stability (99 % activity retention after 35 h), and ultra-high H₂O₂ production yield rate (5.58 mol g_catalyst⁻¹ h⁻¹ in the H-type electrolytic cell), demonstrating its promising industrial application potential. Density functional theory (DFT) reveals that the cyclodextrin-mediated Co(OH)₂ electronic structure optimizes the adsorption of OOH* intermediates and significantly enhances the activation energy barrier for dissociation, leading to the high reactivity and selectivity for the 2 e⁻ ORR. This work offers a valuable and practical strategy to design Co-based electrocatalysts for H₂O₂ production.     

Heteroatom Dopants Promote Two-Electron O2 Reduction for Photocatalytic Production of H2O2 on Polymeric Carbon Nitride

Polymeric carbon nitride modified with selected heteroatom dopants was prepared and used as a model photocatalyst to identify and understand the key mechanisms required for efficient photoproduction of H₂O₂ via selective oxygen reduction reaction (ORR). The photochemical production of H₂O₂ was achieved at a millimolar level per hour under visible-light irradiation along with 100 % apparent quantum yield (in 360–450 nm region) and 96 % selectivity in an electrochemical system (0.1 V vs. RHE). Spectroscopic analysis in spatiotemporal resolution and theoretical calculations revealed that the synergistic association of alkali and sulfur dopants in the polymeric matrix promoted the interlayer charge separation and polarization of trapped electrons for preferable oxygen capture and reduction in ORR kinetics. This work highlights the key features that are responsible for controlling the photocatalytic activity and selectivity toward the two-electron ORR, which should be the basis of further development of solar H₂O₂ production.     

Single-atom Iron Catalyst with Biomimetic Active Center to Accelerate Proton Spillover for Medical-level Electrosynthesis of H2O2 Disinfectant

Electrosynthesis of H₂O₂ has great potential for directly converting O₂ into disinfectant, yet it is still a big challenge to develop effective electrocatalysts for medical-level H₂O₂ production. Herein, we report the design and fabrication of electrocatalysts with biomimetic active centers, consisting of single atomic iron asymmetrically coordinated with both nitrogen and sulfur, dispersed on hierarchically porous carbon (Fe_SA-NS/C). The newly-developed Fe_SA-NS/C catalyst exhibited a high catalytic activity and selectivity for oxygen reduction to produce H₂O₂ at a high current of 100 mA cm⁻² with a record high H₂O₂ selectivity of 90 %. An accumulated H₂O₂ concentration of 5.8 wt.% is obtained for the electrocatalysis process, which is sufficient for medical disinfection. Combined theoretical calculations and experimental characterizations verified the rationally-designed catalytic active center with the atomic Fe site stabilized by three-coordinated nitrogen atoms and one-sulfur atom (Fe-N₃S-C). It was further found that the replacement of one N atom with S atom in the classical Fe-N₄-C active center could induce an asymmetric charge distribution over N atoms surrounding the Fe reactive center to accelerate proton spillover for a rapid formation of the OOH* intermediate, thus speeding up the whole reaction kinetics of oxygen reduction for H₂O₂ electrosynthesis.     

反蛋白石结构ZnO@PDA用于增强光催化产H2O2性能

利用太阳能驱动生产高能量密度的H₂O₂太阳能燃料引起了广泛关注,但目前光催化剂缓慢的动力学限制了其实际应用。本文制备一种聚多巴胺(PDA)改性的反蛋白石结构ZnO(ZnO@PDA)光催化剂,用于可持续性的光催化产H₂O₂。由于电子的转移,因此当PDA与ZnO接触后,会在界面处形成一个从PDA指向ZnO的内建电场。在内建电场和能带弯曲的驱动下,ZnO导带中的光生电子与PDA最高占据分子轨道(HOMO)中的空穴复合,符合梯型异质结的电荷转移和分离途径。这种独特的梯型异质结确保了有效的电子或空穴的分离并且留存下具有强氧化还原能力的光生载流子。此外,与纯ZnO相比,反蛋白石结构的ZnO@PDA具有更强的光吸收能力。实验表明,归因于光吸收能力的提高,光生载流子的有效分离和强氧化还原能力,负载0.03% (原子分数) PDA的ZnO样品具有最佳的产H₂O₂性能(1011.4 μmol·L^-1·h^-1),分别是纯ZnO和PDA的4.4和8.9倍。     

Heteroatom Dopants Promote Two‐Electron O2 Reduction for Photocatalytic Production of H2O2 on Polymeric Carbon Nitride

Polymeric carbon nitride modified with selected heteroatom dopants was prepared and used as a model photocatalyst to identify and understand the key mechanisms required for efficient photoproduction of H₂O₂ via selective oxygen reduction reaction (ORR). The photochemical production of H₂O₂ was achieved at a millimolar level per hour under visible‐light irradiation along with 100 % apparent quantum yield (in 360–450 nm region) and 96 % selectivity in an electrochemical system (0.1 V vs. RHE). Spectroscopic analysis in spatiotemporal resolution and theoretical calculations revealed that the synergistic association of alkali and sulfur dopants in the polymeric matrix promoted the interlayer charge separation and polarization of trapped electrons for preferable oxygen capture and reduction in ORR kinetics. This work highlights the key features that are responsible for controlling the photocatalytic activity and selectivity toward the two‐electron ORR, which should be the basis of further development of solar H₂O₂ production.     

Criegee自由基CH2O2与H2O反应机理及动力学的理论研究

在6-311＋G(2d,2p)水平下, 采用密度泛函理论(DFT)的B3LYP方法, 研究了Criegee 自由基CH₂O₂与H₂O的反应. 结果表明反应存在三个通道: CH₂O₂＋H₂O®HOCH₂OOH (R1); CH₂O₂＋H₂O®HCO＋OH＋H₂O (R2); CH₂O₂＋H₂O®HCHO＋H₂O₂ (R3), 各通道的势垒高度分别为43.35, 85.30和125.85 kJ/mol. 298 K下主反应通道(R1)的经典过渡态理论(TST)与变分过渡态理论(CVT)的速率常数k^TST与k^CVT均为2.47×10^－17 cm³•molecule^－1•s^－1, 而经小曲率隧道效应模型(SCT)校正后的速率常数k^CVT/SCT为 5.22×10^－17 cm³•molecule^－1•s^－1. 另外, 还给出了200～2000 K 温度范围内拟合得到的速率常数随温度变化的三参数Arrhenius方程.     

[Cs(NTO)(H_2O)]配合物的合成及表征

本文首次用碳酸铯与NTO直接合成新的Cs NTO配合物。采用元素分析和化学分析法确定了配合物的组成。用红外光谱法 ,热分析法和X ray粉末衍射法进行了物理化学表征     

Bias-Free Solar-Driven Syngas Production: A Fe2O3 Photoanode Featuring Single-Atom Cobalt Integrated with a Silver-Palladium Cathode

Photoelectrochemical syngas production from aqueous CO₂ is a promising technique for carbon capture and utilization. Herein, we demonstrate the efficient and tunable syngas production by integrating a single-atom cobalt-catalyst-decorated α-Fe₂O₃ photoanode with a bimetallic Ag/Pd alloy cathode. A record syngas production activity of 81.9 μmol cm⁻² h⁻¹ (CO/H₂ ratio: ≈1 : 1) was achieved under artificial sunlight (AM 1.5 G) with an excellent durability. Systematic studies reveal that the Co single atoms effectively extract the holes from Fe₂O₃ photoanodes and serve as active sites for promoting oxygen evolution. Simultaneously, the Pd and Ag atoms in bimetallic cathodes selectively adsorb CO₂ and protons for facilitating CO production. Further incorporation with a photovoltaic, to allow solar light (>600 nm) to be utilized, yields a bias-free CO₂ reduction device with solar-to-CO and solar-to-H₂ conversion efficiencies up to 1.33 and 1.36 %, respectively.     

CuOx/TiO2光催化水蒸气还原CO2

以商品TiO2-P25为原料,通过浸渍法负载一定量过渡金属Cu,得到一系列不同含量的CuOx/TiO2光催化剂。利用X射线衍射（XRD）,X－射线光电子能谱（XPS）,BET,高分辨率透射镜（HRTEM）,X射线荧光光谱（XRF）和光致发光光谱（PL）等方法对催化剂进行了详细表征,在自建的光催化反应器中评价了气态水光催化还原CO2反应的活性和CH4收率。结果表明负载CuOx后的TiO2纳米材料光催化性能显著提高,其中1%CuOx/TiO2样品紫外光照72 h后,CH4生成量达到了24.86 µmol•gTi-1。同时,CuOx负载量、反应温度、反应时间等因素对CH4收率均有显著影响。     

Comprehensive H2O Molecules Regulation via Deep Eutectic Solvents for Ultra-Stable Zinc Metal Anode

The corrosion, parasitic reactions, and aggravated dendrite growth severely restrict development of aqueous Zn metal batteries. Here, we report a novel strategy to break the hydrogen bond network between water molecules and construct the Zn(TFSI)₂-sulfolane-H₂O deep eutectic solvents. This strategy cuts off the transfer of protons/hydroxides and inhibits the activity of H₂O, as reflected in a much lower freezing point (<−80 °C), a significantly larger electrochemical stable window (>3 V), and suppressed evaporative water from electrolytes. Stable Zn plating/stripping for over 9600 h was obtained. Based on experimental characterizations and theoretical simulations, it has been proved that sulfolane can effectively regulate solvation shell and simultaneously build the multifunctional Zn-electrolyte interface. Moreover, the multi-layer homemade modular cell and 1.32 Ah pouch cell further confirm its prospect for practical application.