CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Jun Zhang,Songying Qu,Bing Li,Xiaoyan Li,Lin Lin
The practical use of Fenton process has been thus far limited by the harsh pH and accumulation of iron-rich sludge, while these two shortcomings will be tackled hopefully via developing non-metallic-catalyzed green Fenton-like approach. Herein, we investigate in-situ the dynamic evolution of electrode surface atomic hydrogen (H*) and H* mediated pH-independent and residue-free electro-Fenton process via operando electrochemical investigation and visualization techniques. The H* generated on the surface of palladium-coated electrode enables effective activation of hydrogen peroxide (H 2 O 2 ) to generate hydroxyl radical ( OH) for efficient bisphenol A degradation (>99%), validated by in-situ cyclic voltammetry and electron spin resonance. Meanwhile, in-situ Raman spectra confirms that H 2 O 2 is activated through a transition state of *H 3 O 2 adduct with a low reaction energy barrier of 0.51 eV, whereby the lone electron in H* can readily cleave peroxide bond to produce OH and H 2 O as the only products ( ΔG = −1.03 eV). More importantly, the electron-driven H* production is independent of the solution pH as both H + and H 2 O can act as precursors verified by in-situ fluorescence analyses, so that the H 2 O 2 activation mediated by H* extends successfully to a wider pH range (3–10). Our research provides a promising path toward eliminating restrictions of traditional Fenton process and paves the way simultaneously for in-situ investigation into reaction mechanism of such electrochemical processes.
研究领域:
环境科学
·
电化学
✓ 已验证
DOI
高影响因子
Chem
·
2025
·Vol. 12
·期 3
·
IF 19.6
Yu-He Liang,Jia-Xin Kang,Yan Wang,Yi-Ge Li,Hou-Ji Cao,Qianyi Zhao,Xuenian Chen,Yan-Na Ma
The selective B–H functionalization of carboranes has received considerable attention because of their wide applications in functional materials, catalysis, and pharmaceuticals. Deuterium-labeling experiments and kinetic-isotope-effect experiments are two important tools for mechanistic studies on the selective B–H activation of carboranes. Thus, developing an effective method for the synthesis of perdeuterated carboranes is highly desirable. Herein, we present a practical method for synthesizing perdeuterated carboranes via Pd(II)-catalyzed B–H activation by using D 2 O as a deuterium source. This protocol features extraordinary functional-group tolerance, high levels of deuterium incorporation, and ease of scaling. Mechanistic studies illustrate that the deuteration reaction proceeds via Pd(II)-catalytic electrophilic H/D exchange and subsequent intermolecular Pd migration. The same degree of deuterium incorporation across all boron vertices indicates that the Pd-migration step is faster than the electrophilic palladation step. Additionally, the versatility of this method is reflected in the deuteration of other boron clusters.
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Zhenglin Chen,Guangzhen Liu,Shuiping Yu,Lixia Yang,Lingyi Zheng,Zhihui Wei,Shenglian Luo
Cathode materials with high hydrogen peroxide (H 2 O 2 ) selectivity and Fe 2+ regeneration under macroneutral conditions are the essential for practical electro-Fenton processes. Herein, we develop an amorphous cobalt sulphide (CoSx(t = x)@Cu) cocatalytic electro-Fenton (EF) system capable of effectively degrading organic pollutants, such as sulfamethoxazole, at macroneutral pH conditions. Owing to the flexible electronic properties of amorphous structures and charge redistribution triggered by S defects, the optimum CoSx(t = 8)@Cu cathode successfully introduces H*/H + and promotes the in-situ evolution of H 2 O 2 . Additionally, an acidic microenvironment was constructed on the CoSx(t = 8)@Cu surface by the unreduced H*/H + , enabling a self-adjustment from alkalinity to acidity in the EF reaction without adding acid. Such self-adjustment effectually inhibits iron sludge production and promotes Fe 2+ regeneration, assuring 80% Fe 2+ cycling efficiency. More importantly, the EF system possesses outstanding stability and applicability for organic pollutant remediation regardless of water matrices. This work elucidates the intrinsic mechanism of amorphous electrocatalysts in overcoming the pH limitation of EF reactions, extending the applicability of Fenton technology.
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2020
·
IF 12.35
Shengbo Zhang,Mei Li,Lisheng Li,Fabrice Dushimimana,Jiankang Zhao,Shuai Wang,Jinyu Han,Xinli Zhu,Xiao Liu,Qingfeng Ge,Hua Wang
Regulating electron density at the active site by integrating contributions from multiple channels is an effective strategy to accelerate the reaction rate. Herein, the hydrolysis of ammonia borane (AB) is systematically studied on the NiCu alloy-loaded carbon nitride nanosheets (NixCuy/CNS). The TOF of AB hydrolysis for NiCu/CNS catalyst under visible light irradiation was nearly 3.5 times higher than that in the dark. Photoelectrochemical characterizations indicate that the improved photocatalytic activities originate from a combination of alloying effect, Mott–Schottky junction at the metal–semiconductor interface as well as the localized surface plasmon resonance induced under the visible light irradiation, which synergistically increase the local electron density at the active Ni sites. More importantly, the infrared spectra and isotope labeling-mass spectrometry methods were used to establish the source of hydrogen and unravel the reaction mechanism. It is suggested that the cleavages of B–H and O–H bonds are the initial steps of AB hydrolysis, which lead to the formation of intermediates M–H– (metal and electronegative H– from −BH3) and M–H+ (metal and electropositive H+ from H2O), respectively. The H2 molecule could form through three main paths as (1) two H atoms from −BH3, (2) two H atoms from H2O, and (3) one H atom from −BH3 and another from H2O. Results of density functional theory (DFT) calculations are consistent with the formation of electron-rich Ni sites in the NiCu, and the activation of H2O is a rate-limiting step (RLS). Redistribution of electrons in NiCu significantly enhances the adsorption of AB, the activation of H2O molecules, and the associative desorption of H adatoms as well, which effectively promote the cleavage of B–H and O–H bonds and release of H2. This work gives a systematic mechanistic study on photocatalytic AB hydrolysis involving multichannel electron-transfer pathways, which will provide a powerful guidance for the rational design of active catalysts for AB hydrolysis through multipronged effects.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2023
·
IF 9.9
Jia'ni Gong,Pengfei Bai,Yifu Zhang,Qiushi Wang,Jingjing Sun,Yanyan Liu,Hanmei Jiang,Ziyi Feng,Tao Hu,Changgong Meng
Molybdenum trioxide (MoO 3 ) has been widely studied in the energy storage field due to its various phase states and unique structural advantages. Among them, lamellar α -phase MoO 3 ( α -MoO 3 ) and tunnel-like h -phase MoO 3 ( h- MoO 3 ) have attracted much attention. In this study, we demonstrate that vanadate ion (VO 3 - ) can transform α -MoO 3 (a thermodynamically stable phase) to h -MoO 3 (a metastable phase) by altering the connection of [MoO 6 ] octahedra configurations. h -MoO 3 with VO 3 - inserted (referred to as h -MoO 3 -V) as the cathode material for aqueous zinc ion batteries (AZIBs) exhibits excellent Zn 2+ storage performances. The improvement in electrochemical properties is attributed to the open tunneling structure of the h -MoO 3 -V, which offers more active sites for Zn 2+ (de)intercalation and diffusion. As expected, the Zn// h -MoO 3 -V battery delivers specific capacity of 250 mAh·g −1 at 0.1 A·g −1 and rate capability (73% retention from 0.1 to 1 A·g −1 , 80 cycles), well exceeding those of Zn// h -MoO 3 and Zn// α -MoO 3 batteries. This study demonstrates that the tunneling structure of h -MoO 3 can be modulated by VO 3 - to enhance the electrochemical properties for AZIBs. Furthermore, it provides valuable insights for the synthesis, development and future applications of h -MoO 3 .
✓ 已验证
DOI
PubMed
高影响因子
Journal of Environmental Sciences
·
2025
·
IF 6.3
Likai Wang,Donglin Liu
The degradation of persistent organic pollutants like 4-chlorophenol (4-CP) remains a critical challenge in wastewater treatment. Transition-metal sulfides have emerged as promising Fenton-like catalysts owing to their tunable electronic structures and abundant redox-active sites. Herein, we report a highly efficient Fenton-like system using ternary copper-iron sulfide (Cu x Fe y S z ) nanocatalysts for 4-CP degradation. Three Cu x Fe y S z phases—CuFe₂S₃, CuFeS₂, and Cu₅FeS₄—were synthesized and systematically evaluated, with CuFe₂S₃ demonstrating superior catalytic activity, achieving complete degradation of 20 mg/L 4-CP within 7 min using 5 mmol/L H₂O₂. Mechanistic studies reveal that sulfur vacancies in CuFe₂S₃ serve as key features, enhancing H₂O₂ adsorption and activation, as evidenced by in situ Raman spectroscopy. Comparative studies with CuFe₂S₃ analogues (0.7-CuFe₂S₃, 0.9-CuFe₂S₃, Fe₃S₄, and Cu₈S₅) confirm the unique catalytic efficiency of stoichiometric CuFe₂S₃, attributed to its optimal electronic structure and vacancy density. This work not only presents CuFe₂S₃ as a cost-effective and high-performance Fenton-like catalyst but also lays a solid foundation for the application of naturally occurring copper-iron sulfide minerals in wastewater treatment.
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2026
·Vol. 16
·期 14
·13525-13536
·
IF 13.6
Wang Yue,Zhang Qi,Han Chunqiu,Jia Wenlong,Liu Huai,Zhang Rui,Peng Lincai,Lv Tianping,Ye Liqun,Zhang Junhua
Photocatalytic activation of C–H bonds in biomassderived molecules represents a promising strategy for biomass
upgrading. However, the efficiency of selective C–H bond activation
and oxidation is severely restricted by the sluggish kinetics of photogenerated carriers and the uncontrollable generation of reactive oxygen species. Herein, we delicately dispersed Yb single atoms on
ZnIn2S4 nanosheets that boost the photocatalytic directional activation of C–H in 5-hydroxymethylfurfural (HMF). The optimized
Yb0.8-ZIS achieves a balance between 2,5-diformylfuran selectivity
(99.8%) and production rate (906.6 μmol g–1 h–1
) under ambient
conditions. Mechanistic studies reveal that Yb single atoms not only
effectively modulate the electronic structure of ZnIn2S4 but also
serve as hole extractors, thereby enhancing the separation of photogenerated carriers and the activation of oxygen. Furthermore, the ligand-to-metal charge transfer between Lewis acidic Yb sites and
HMF effectively reduces the electron density of the α-C–H bond, thus accelerating the activation process. This work offers insight
into the rational design of rare-earth single atoms for modulating both charge dynamics and molecular activation in selective C–H
activation and oxidation.
KEYWORDS: Yb single-atom, C–H activation, electronic structure, photocatalytic oxidation, 5-hydroxymethylfurfural
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2026
·
IF 18.1
Zhang Mengen,Wang Ruijia,Yu Yunbo,Ren Liuxuan,Jia Tinghao,Ren Congjing,Wang Jingdai,Yang Yongrong,Yang Yao
C-H functionalization shows significant potential for upgrading low-cost semi-crystalline polyolefins. However, current homogeneous functionalization methods encounter an inherent trade-off between crystallinity and functionalization, severely limiting the application of resulting functional polyolefins in both emerging and previously established fields. Here, we demonstrate an electrostatic-confinement-induced C-H functionalization strategy that decouples the functionalization from the crystallinity of resultant functionalized polyolefins in a well-controlled manner. During functionalization, multivalent cations spatially confine electronegative polar functional groups within amorphous domains through electrostatic interactions. This enables highly selective functionalization of amorphous regions at temperature approaching the melting point, yielding functionalized polyethylene exhibiting a higher crystalline fraction, larger crystallite dimensions, and distinct nanoscale sheet-like aggregates of incorporated polar groups. These structural improvements elevate melting temperatures and impart mechanical property enhancement to a typical prototype. This strategy highlights the potential for overcoming traditional crystallinity-functionalization trade-offs in post-polymerization functionalization and offers promising avenues for advanced materials development with target properties.
✓ 已验证
DOI
PubMed
高影响因子
ACS Catalysis
·
2026
·
IF 13.6
Keying Li,Bo Gao,Song Xu,Qun Xu
Abstract Electrocatalytic reduction of nitrate (NO3–) is highly desired for the synthesis of value-added nitrogenous compounds, where precise selectivity control remains as a key challenge to be tackled. In addition to catalyst composition, electrolyte microenvironment offers another feasible handle for selectivity regulation, where the interfacial H-bond network could be effectively tuned for directed H-atom transfer for selectivity manipulation. Herein, two molecules with distinct molecular configurations, oxalic acid (OA) and acetic acid (HOAc), were introduced into the electrolyte microenvironment to investigate the in-depth structure-functional relationship between electrolyte structure and electrocatalytic NO3– selectivity, where vicinal H-bond acceptors (carboxylic groups) makes OA an ideal “molecular glue” to fortify the H-bond network for H atom transfer. As a result, OA significantly facilitates electrocatalytic NO3– hydrogenation, leading to efficient production of NH2OH (219 μmol·cm–2·h–1, 78.2%). Contrastingly, partially hydrogenated NO2– is characterized as the major product upon HOAc introduction (284.4 μmol·cm–2·h–1, 82.4%), which lacks vicinal carboxylic groups for H-bond network fortification. The NH2OH and NO2– products were effectively converted to formaldoxime and nitrophenol, which extended the directed electrocatalytic NO3– conversion toward synthetic applications.
✓ 已验证
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2021
·
IF 3.764
Liyuan Li,Tao Li,Yifan Sha,Chi Zhang,Baozeng Ren,Lan Zhang,Suojiang Zhang
Silicon-based anode materials attract ever-increasing attention owing to their high theoretical capacity. However, their practical application is significantly hindered by the dramatic volume change during the charge/discharge process, during which not only the solid electrolyte interface (SEI) but also the electrode might be ruined. Here, we propose a H-bond network-regulated binder by introducing low-molecular-weight cross-linkers, lithium oxalate and α-cyclodextrin (α-CD), into alginate (Alg). The balance between the binding strength and Li ion diffusion is realized through the control of the ratio between them. Lithium oxalate and α-CD can effectively regulate the H-bond network of the binder by forming intermolecular dynamic H bonds with Alg and reducing the intramolecular ones. Although the hybrid binder shows lower adhesion force than Alg, better electrode integrity is obtained during the charge/discharge process. Meanwhile, Li+ transportation is facilitated due to extra Li+ supplied by lithium oxalate, thereby achieving better rate capability.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Yuyao Sun,Yi Han,Xinyi Zhang,Wenwen Cai,Yanyun Zhang,Yan Zhang,Zhenjiang Li,Bin Li,Jianping Lai,Lei Wang
Titanium dioxide (TiO 2 ) is widely used as a representative transition metal oxides (TMOs) catalyst for electrocatalytic nitrogen reduction reaction (NRR). However, the low stability, low selectivity, low ammonia (NH 3 ) yield and high overpotential of TiO 2 towards NRR strongly restricted its application in NRR. Here, we firstly add H to the lattice to synthesize a black TiO 2−x with oxygen vacancies (OVs) (B-TiO 1.8 ) for electrocatalytic NRR. After we optimized the amount of H and OVs, the NH 3 yield and stability can achieve 31.6 μg h −1 mg cat −1 and 100 h at − 0.1 V ( vs . RHE), respectively, the faradaic efficiency (FE) can achieve 47.7% at 0 V ( vs . RHE). In situ FTIR / ESR / XPS / TPD illustrate that OVs can promote the adsorption and activation of nitrogen (N 2 ), and lattice H can increase the number of OVs and stabilize them, suppress the hydrogen evolution reaction (HER) and promote the hydrogenation of N 2 .
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER RESEARCH
·
2019
·Vol. 26
·期 12
·1-9
·
IF 1.53
Chen Jiewei,Shang Jingqi,Xue Feng,Wei Qiushi,Xu Ning,Ding Enyong
This article reports on the high-efficiency preparation of few layers h-BN nanosheets (BNNSs) by a high-pressure homogenizer. Then, the BNNSs/chitosan microspheres (BN-CS-M) are finally prepared by mixing BNNSs with chitosan under alkaline conditions. The BNNSs dispersion is investigated by UV-vis spectrophotometer and Transmission Electron Microscopy. In addition, we use Scanning Electron Microscopy and Laser particle size analyzer to characterize the microscopic and macroscopic morphology of BN-CS-M composites. Raman spectroscopy and Specific surface area testing are also used to explore the intrinsic properties of BN-CS-M. Thermal gravimetric analysis shows that composites with high content of BNNSs possess higher thermal stability. The results show that BNNSs is dispersed in the network of chitosan microspheres, and the higher the rate of centrifugation, the fewer BNNSs dispersed in the microspheres. The chitosan microspheres composite with pore diameters in the range of 1.7–2.9 nm belongs to the type IV adsorption curve.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）