CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Xitong Yang,Guowei Liu,Ruifeng Zhou,Zhengzheng Xie,Yamin Cheng,Muhammad Shuaib Khan,Qiuye Li
Catalytic desorption can reduce the activation energy of the reaction and increase the desorption reaction rate, and is one of the most promising technologies to solve energy consumption problems of CO 2 capture technology for organic amine solutions. In order to further reduce desorption energy consumption, we propose a new method of utilizing the photothermal effect of catalysts to increase desorption temperature and accelerate reaction kinetics, and coupling the proton transfer ability of the catalyst itself to form multifunctional catalysis. In this work, we synthesized Ru x Mn 1-x OOH catalyst by introducing Ru atoms at the Mn vacancies on the MnOOH surface, grasping the advantages of the photothermal and proton transfer ability of Ru-dopants. The results showed that the CO 2 desorption capacity increased by 43.1% with adding MnOOH compared to without a catalyst. The Ru-doped catalyst demonstrated a 54.7% increase in CO 2 desorption efficiency, with an additional 98.2% surge attributed to the in-situ photothermal effect generated by the catalyst under light irradiation. Characterization and density functional theory (DFT) calculations revealed that Ru doping significantly enhanced the proton transfer ability while simultaneously weakens the adsorption capacity of monoethanolamine (MEA) on the catalyst surface. Moreover, the stronger photothermal effect introduced by Ru leads to an increase in the surface temperature of the catalyst, which is key to the faster and efficient desorption of CO 2 . This work provides a new approach to improve the proton transfer ability of catalysts and offers a novel photothermal coupled catalytic scheme for CO 2 desorption in organic amine carbon capture technology.
研究领域:
化学工程
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催化材料
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环境科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Nana Zhou,Yurong Yin,Baojuan Luo,Yongxin Fu,Xiaoxun Ma,Chengyi Dai
The electrochemical CO 2 reduction reaction (eCO 2 RR), which is well suited for reducing atmospheric CO 2 levels and generating clean energy. Water is the main proton source in the electrochemical reduction process. However, water features a high dissociation energy barrier, and most protons are involved in HER, so that only a small amount of H + is used in the CO 2 reduction reaction. Herein, we reveal that appropriately chosen ligands on the catalyst surface can abstract protons from water, store them, and transfer them to CO 2 to promote the formation of COOH and improve the proton utilization efficiency of the eCO 2 RR. Moreover, the activity of the ligand complexed protons is shown to be lower than that of free ones and thus result in HER inhibition our ligands with different pK a values (i.e., proton release capacities) are used to functionalize ZnO, and the plot of pK a vs. the FE CO exhibits a volcano shape. Overly small pK a leads to the combination of abundant protons with each other and the dominance of the HER, whereas overly large pK a does not promote the utilization of H + by CO 2 . Ligands with suitable pK a can properly bind and release protons, which is conducive to the formation of *COOH, thus accelerating eCO 2 RR. In particular, mercaptobenzoic acid (MBA) considerably enhances catalytic activity because of its moderate pK a (FE CO = 90 %, which is 2 times higher than the FE CO of unmodified ZnO, and j CO is nearly 5 times higher). In situ infrared spectroscopic analysis proves that the above ligand can abstract protons from H 2 O and then release them, promoting the dissociation of H 2 O. Theoretical calculations show that pK a affects the ability of ligands to abstract and release protons.
研究领域:
材料科学
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电化学
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催化反应
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DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
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2022
·Vol. 25
·期 1
·402-409
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IF 3.945
Ran Wang,Fengjin Zhang,Xinghang Pan,Xuming Zheng,Jiadan Xue,Yong Du,Binbin Xie
8-Hydroxy-5-nitroquinoline (NO2-QN-OH) is an antimicrobial, anti-inflammatory and anticancer agent, and has been approved for use in the treatment of diseases. Its photosensitivity, however, cannot be overlooked. The photochemistry of 8-hydroxy-5-nitroquinoline in acetonitrile is investigated using transient absorption and time-resolved resonance Raman spectroscopies. By identifying the short-lived intermediates during the photoreaction, it is clear that the Tn state NO2-QN-OH is generated in 0.8 ps via an ultrafast ISC, followed by the IC in 8.5 ps to produce the T1 state. In neat acetonitrile, the T1 state NO2-QN-OH undergoes intramolecular proton transfer and tautomerizes to form T1 state NO2-QNH-O. To our knowledge, this is the first time that the intramolecular excited state proton transfer of hydroxyl-quinolines in an aprotic polar solvent is observed.
研究领域:
光化学
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物理化学
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光谱学
✓ 已验证
DOI
高影响因子
ACS ES&T Water
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2025
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IF 4.3
Xuecong Qian,Luwei Li,Jinhao Duan,Shilong Wang,Yun Liu,Da Wang,Haijun Cheng,Jun Ma
In aqueous systems, Mn(II) oxidation by chlorine involves both electron and proton transfer. However, the slow proton transfer due to water molecule’s limited proton acceptance capacity leads to low Mn(II) oxidation efficiency under near-neutral conditions. Pyridine (pKa = 5.25), a strong proton acceptor, was selected to investigate electron–proton transfer principles in Mn(II) oxidation. Kinetic studies show that pyridine enhances Mn(II) oxidation efficiency by chlorine under neutral to alkaline conditions (pH 7.0–9.5), with maximal enhancement observed when pH approaches pyridine’s pKa. A high kinetic isotope effect (up to 6.9) and an E1/2-pH slope near the Nernstian value in cyclic voltammetry experiments confirm that pyridine induces a concerted electron–proton transfer (CEPT) pathway. Density functional theory calculations reveal that the pyridine-induced CEPT pathway is thermodynamically more favorable than stepwise electron transfer followed by proton transfer (ETPT) and proton transfer followed by electron transfer (PTET) pathways, explaining the enhanced oxidation efficiency. Similarly, in pyridine-free systems, increasing pH from 7.0 to 9.5 promotes Mn(II) oxidation efficiency through an OH–-mediated pathway switching from ETPT to PTET and CEPT pathways. This study demonstrates the controlling role of proton transfer in the Mn(II) oxidation process, providing theoretical guidance for the rational selection or design of Mn-removal catalysts.
研究领域:
环境化学
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物理化学
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无机化学
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化学动力学
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电化学
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理论化学
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产品关联
DOI
高影响因子
JOURNAL OF CHEMICAL PHYSICS
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2024
·Vol. 160
·期 24
·
IF 3.1
Wang Ye,Wang Dongdong,Hu Xiao,Zhang Song
The ultrafast proton transfer and the following dynamics for aromatic Schiff bases N , N ′-bis(salicylidene)ethylenediamine (salen) and N , N ′-bis(salicylidene)-1,4-butylenediamine (salbn) were investigated with experimental and theoretical methods. A dual emission property with a large Stokes shift in salen and salbn indicates that excited state intramolecular proton transfer occurs with photoexcitation. An efficient single proton transfer was confirmed within 200 fs for both molecules. Subsequently, a fast twisted motion of the keto moiety carries cis -keto to a relaxed stable geometry in the S 1 state. Following the twisted motion, the phenol ring at keto moiety further rotates to a conical intersection with the ground state and a cis – trans isomerization occurs. The isomerization rate is high, which dominates the competition with the radiative transition, resulting in weak emission intensity. It is confirmed that the length of alkyl chain affects the direction of phenol ring twisting and rotation during the whole subsequent relaxation of excited cis -keto tautomer. Compared with polar solvent acetonitrile, the barrier of isomerization is higher and the hydrogen bond on keto moiety is stronger in nonpolar solvent toluene. It makes fluorescence radiation channels competing with isomerism more likely to occur, contributing to the observed difference of enol/keto emission ratios of salen and salbn in toluene and acetonitrile.
研究领域:
物理化学
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理论化学
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光化学
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DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
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2018
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IF 5.667
Long Yu,Yingyun Li,Huan Yu,Kui Zhang,Xiaowan Wang,Xinfeng Chen,Ji Yue,Tianxi Huo,Hongwei Ge,Khalid A. Alamry,Hadi M. Marwani,Suhua Wang
Ozone is widely used in air sterilization, food and medical disinfection in modern society, but high ozone levels in the living environment are considered harmful and have been associated with various respiratory diseases. Therefore, quick detection for ozone of part per million (ppm) levels is significant for living environment and an excited-state intramolecular proton transfer (ESIPT) compound has been synthesized. Due to an intrinsic excited-state intramolecular proton transfer (ESIPT) process, this “off-on” probe can fluoresce in the solid-state. This intrinsic fluorescent property makes it easy to detect lower concentration of ozone since the reaction product of probe can avoid being affected by pH and solubility through luminescence in the solid-state. The limit of gaseous ozone detection can be as low as 0.28 ppm for obviously distinguishable fluorescence colour from blue to cyan, showing that the probe can be useful for detecting ozone without the need of elaborate equipment.
研究领域:
环境科学
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分析化学
✓ 已验证
DOI
高影响因子
Green Energy & Environment
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2025
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IF 14.6
Xiang Hui,Jianhui Shi,Jiajun Zhang,Yan Cao,Huiquan Li,Peng He,Liguo Wang
The carbonylation of amines offers a promising route for synthesizing N-substituted carbamates with high atom economy. However, conventional catalysts exhibit limited catalytic efficiency, and the underlying proton transfer mechanism remains elusive. Herein, we reported a metal-free, room-temperature strategy utilizing 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a dual hydrogen bond catalyst to synergistically activate propylamine (PA) and dimethyl carbonate (DMC). This green catalytic system achieves a 10-fold acceleration in reaction rate compared to other hydrogen bonding catalysts under mild conditions. This is enabled by dual hydrogen bonding of TBD with PA and DMC, which facilitates rapid proton transfer and stabilizes tetrahedral intermediates. Theoretical calculations confirm that the dual hydrogen bond system significantly lowers activation energy compared to single hydrogen bond analogs. Furthermore, it was revealed that the hydrogen bonding network within the product is the primary factor responsible for the sluggish reaction rate. This study demonstrates the effectiveness of a dual hydrogen bond system in accelerating the carbonylation of amines and provides a green route to access carbamates.
研究领域:
化学
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催化科学
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有机合成
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产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2024
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IF 4
Zijuan Wang,Shuimei Shen,Junjie Peng,Da Wu,Xinyue Liu,Mingkang Xu,Xiangjun Shi,Weike Su
The development of solid-state forms of drugs is an effective approach to increase solubility. This study developed three crystalline complexes of sorafenib (SF) with oxalic acid (OA) and malonic acid (MA) using a solvent method, named SF + ·OA - ·THF, SF + ·OA - , and SF-MA. The formation of these complexes was influenced by the crystalline method, solvent polarity, and the carbon chain length of the dicarboxylic acids. Single-crystal X-ray diffraction revealed proton transfer in SF + ·OA - ·THF, classifying it as a channel-type salt solvate and conformational polymorph due to hydrogen bond formation. 13 C solid-state nuclear magnetic resonance and X-ray photoelectron spectroscopy confirmed proton transfer in SF + ·OA - ·THF and SF + ·OA - , but not in SF-MA, indicating that SF + ·OA - is a salt while SF-MA is a co-crystal. Fourier Transform Infrared Spectroscopy further supported these findings. Compared with Form Ⅰ, SF + ·OA - , SF + ·OA - ·THF, and SF-MA increased the apparent solubility of SF by 8.3, 7.9, and 6.4 times in pH 1.2 HCl buffer, and by 4.0, 3.1, and 4.5 times in pH 6.8 PBS buffer, respectively. All crystalline complexes exhibited a “spring and parachute” phenomenon due to the solubility difference between the drug and the dicarboxylic acids. Notably, the intermolecular forces between SF and THF in SF + ·OA - ·THF prolonged the “spring and parachute” process. Additionally, these crystalline complexes demonstrated good stability. This study provides valuable insights into the development and identification of crystalline complexes and their dissolution mechanisms.
研究领域:
药学
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材料科学
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2021
·
IF 9.229
Chenghan Ji,Hang Yu,Junhe Lu,Yi Ren,Lu Lv,Weiming Zhang
Adsorption as a desalination approach has the advantages of energy efficiency, low cost, and operational convenience, but its practical application is limited by low desalination capacity, consumption/disposal of strong acids/bases as regeneration reagents, and poor reusability. Herein, we synthesized a thermo-regenerable salt absorbent by grafting ethylenediaminetetraacetic acid (EDTA) onto a metal–organic framework (MOF), MOF-808-EDTA, which could rapidly adsorb NaCl within 30 min from saline water at 25 °C with a desalination capacity as high as 9.4 mmol/g. Moreover, the saturated adsorbent could be facilely regenerated in 80 °C water. Fourier transform infrared spectroscopy and derivative thermogravimetry revealed that temperature-regulated proton transfer between amino and carboxyl groups was the mechanism of thermo-regeneration. EDTA on MOF-808-EDTA appears in a zwitterionic state in water at room temperature, which allowed simultaneous adsorption of Na+ and Cl–. At elevated temperature, it returned to a nonionic state accompanied by the desorption of ions. A similar temperature-dependent adsorption–regeneration process was also observed for other salts, including LiCl, KCl, CaCl2, and MgCl2. Column experiments of brackish groundwater showed that 1 g of MOF-808-EDTA could produce ∼106 mL of fresh water (total dissolved solids < 600 mg/L) without significant capacity loss after 10 successive adsorption–regeneration cycles. This study is the first to propose an EDTA-based MOF for desalination and indicates the potential of MOF-808-EDTA as a green adsorbent for sustainable water desalination.
研究领域:
材料科学
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环境科学
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化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
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2024
·
IF 4
Qianqian Xing,Xiaoliang Jia,Shiyu Jia,Yongqin Qi,Yuqi Wang,Yingxiong Wang,Xianglin Hou
The traditional synthesis methods of cyclopropyl methyl ketone (CPMK) have some disadvantages such as low yield, slow reaction rate and unclear catalytic mechanism. To solve these problems, a new strategy is developed to synthesize CPMK from 5‑chloro-2-pentanone (CPE) using 1,8-diazabicyclo[5.4.0]undec‑7-ene (DBU). Experiment results show that the yield of CPMK reached a maximum of 96.5 % in DBU at 40 °C for 30min. The mechanism study shows that the hydrogen bond between DBU and CPE is the key to drive the deprotonation and cyclization of CPE. The hydrogen bond is formed between the N atom on C = N of DBU and the α-H on the methylene group associated with the carbonyl group on CPE. The catalyst DBU is converted into [DBUH] + Cl − , which can be reclaimed and recycled completely. The density functional theory (DFT) calculation confirmed the existence of molecular hydrogen bonds and proved that the hydrogen bond driving force is the key to the reaction. The hydrogen bond driven mechanism provides a new idea for the basic research of cyclization reaction.
研究领域:
有机化学
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催化反应
✓ 已验证
产品关联
DOI
高影响因子
WATER RESEARCH
·
2024
·
IF 11.4
Shiyu Zuo,Yan Wang,Jinquan Wan,Jianxin Yi
A fundamental scientific quandary in environmental has always been the pH dependence in Fenton reaction, that is, the reaction kinetics decreases by approximately 1–3 orders of magnitude upon transitioning from an acidic to an alkaline state. Here, we discovered that protons significantly contribute to the Fenton reaction through an examination of the reaction's interfacial behavior characteristics. Proton transfer mediated by hydrogen bond network connectivity in the electric double layer is responsible for the pH dependence of Fenton reaction kinetics. On this basis, the surface potential of Fenton reaction catalyst was modified to optimize the distribution of H 2 O in the electrical double layer, enhancing the connectivity of the interfacial hydrogen bond network and providing a fast channel for rapid proton transfer. The consecutive hydrogen bond network mediates rapid proton hopping, increasing the proton concentration in the Helmholtz layer, and consequently promoting the proton conductivity from 5.38×10 −7 S·cm −2 to 4.35×10 −6 S·cm −2 in alkaline conditions for Fenton reaction. Meanwhile, the kinetics reaction rate was improved 20 times, and the pH dependence was reduced from 70.9 % to 12.6 %. This discovery clarifies the key role of the interfacial hydrogen bond network and proton transfer in Fenton reaction kinetics pH dependence. It provides new theories and methods for achieving alkaline high Fenton reaction kinetics.
研究领域:
环境科学
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化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS
·
2019
·
IF 2.705
Rui Wang,Yao Cheng,Yanan Xie,Jie Li,Yinliang Zhang,Zemin Fang,Wei Fang,Xuecheng Zhang,Yazhong Xiao
Laccases (benzenediol: oxygen oxidoreductases , EC1.10.3.2) can oxidize wide range of compounds thus have great application potential in diverse industries. The catalytic mechanisms of laccases have been extensively studied, while the details of proton transfer remain to be fully elucidated. In this study, we tried to uncover the sites that are crucial for the proton transfer of microbial laccase Lac15. A residue near the trinuclear copper center, D396, was indicated by statistical coupling analysis (SCA) and structural alignment to be an important site like D93, which is conserved in laccases and believed crucial for the catalysis by facilitating proton transfer. A representative mutant at this site, D396A, similar to D93A, exhibited significantly impaired catalysis with the global structure and substrate binding slightly perturbed. The mutation resulted in stay of the intermediate I, which would accept a proton to proceed to next catalysis stage, suggesting D396 might play a critical role in the proton transfer. Our finding may help to completely elucidate the proton transfer mechanism in laccases.
研究领域:
生物化学
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酶学
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结构生物学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）