ChemistrySelect
·
2024
·Vol. 9
·期 13
·e202303633
·
IF 1.9
Mingyan Chen,Wentao Wang,Xinkai Feng,Dehua Zhang,Yao Zhang,Yucheng Liu
Graphical This work describes the application of a highly efficient catalyst (NH 2 -UiO-66-Mo) to the catalytic oxidation desulfurization process. NH 2 -UiO-66-Mo can greatly improve the efficiency of oxidative desulfurization The optimum operating conditions of NH 2 -UiO-66-Mo are investigated through experiments, which prove the excellent performance of the catalyst, and the reaction mechanism is further studied through a series of characterizations. A highly efficient oxidative desulfurization composite catalyst NH 2 -Uio-66-Mo has been prepared and applied in the catalytic oxidative desulfurization. It was elucidated that Mo 6+ could increase the oxygen vacancies and active sites on the catalyst and increase the pore size of UiO-66. Meanwhile, the removal rate of dibenzothiophene (DBT) reached 99.2 % after 60 min under optimal conditions and remained above 90 % after 5 cycles, showing the composite catalyst's remarkable catalytic performance and satisfactory reusability NH 2 -UiO-66-Mo. In addition, kinetic studies revealed that the desulfurization process can present a pseudo-first-order kinetic process. The apparent activation energy was 10.6 kJ/mol. Finally, in combination with oxides, possible oxidation pathways were identified.
✓ 已验证
产品关联
DOI
高影响因子
Journal of Energy Storage
·
2022
·
IF 8.907
De-Ming Zhu,Fan Bai,Yi-Nan Zhang,Ya-Nan Yang,Zhuang Sun,Jun-Wen Deng,Tao Zhang
Solid-state Li-O 2 batteries (SSLOBs) have been denoted as the holy grail in next-generation Li metal batteries for their high theoretical energy density , manipulation of ambient air to energy storage as well as high safety. However, the solid rigid interfaces both at the cathode and anode side introduce ultra-high resistances in the battery system and impede its operation under ambient temperature. Moreover, the high-reductive Li anode and semi-open cathode would cause severe side reactions during cycling which further degrade battery performance. To manage the above-mentioned issues, a rationally designed SSLOBs based on plastic crystal electrolyte is proposed in this study to enable SSLOBs operation at ambient temperature and in full charge-discharge mode. The brand-new Li-O 2 battery has been improved mainly from two aspects. First, we propose a polyacrylonitrile (PAN) modified succinonitrile (SN) electrolyte (PAN-SN) to retard the polymerization of SN and meanwhile suppress the degradation of Li ionic conductivity. Second, we propose an alternative mixed electron/ion complex conductor (MEIC) cathode to coordinate with plastic crystal electrolyte with an expanded Li-O 2 reactive zone and improved interfacial charge transfer during the charge-discharge process. The fabricated flexible SSLOBs based on PAN-SN electrolyte and MEIC cathode could be successfully fully charged-discharged (cutoff 2.0–4.5 V) for tens of cycles at ambient temperature under simulated air condition (20 vol% oxygen), with high-capacity retention of around 85 %.
研究领域:
能源存储
·
电池技术
·
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF ANALYTICAL CHEMISTRY
·
2020
·
IF 0.936
Liang WANG,Zhang-Quan PENG
Development of lithium-oxygen (Li-O 2 ) batteries is hindered by large overpotentials, low energy efficiency and unsatisfactory cycling life, which are predominately caused by the oxygen evolution reaction (OER) involving sluggish oxidation of lithium peroxide (Li 2 O 2 ). Herein, a highly-efficient soluble redox mediator (RM) of N , N’ -Diphenyl- p -phenylenediamine (DPPD) is introduced to catalyze the oxygen evolution reaction for Li-O 2 batteries. During charging process, DPPD is electrochemically oxidized into DPPD + , which can chemically decompose Li 2 O 2 on the cathode with a much-reduced overpotential. The in-situ differential electrochemical mass spectrometry confirms that the charging process is dominated by Li 2 O 2 decomposition. With the assistance of DPPD, Li-O 2 cells can achieve lower charging potential, improved cycling stability, and prolonged lifespan (294 cycles) which is three times longer than that of tetrathiafulvalene counterpart. This work presents a credible and viable opportunity for long lifespan Li-O 2 batteries.
研究领域:
电化学
·
能源材料科学
✓ 已验证
DOI
高影响因子
NANOTECHNOLOGY
·
2019
·Vol. 30
·期 36
·364003
·
IF 3.399
Chao Li,Yijie Liu,Bojie Li,Fan Zhang,Zhu Cheng,Ping He,Haoshen Zhou
All-solid-state Li–O2 batteries are receiving intense interest because of the substitution of solid electrolytes for toxic and flammable liquid electrolytes. However, new issues are arising in the aspect of the electrolyte cathode interface. On the one hand, in a traditional sandwiched battery structure, the reaction sites of the cathode are restricted to the finite planar electrode–electrolyte interface, resulting in limited performance of all-solid-state Li–O2 batteries. On the other hand, integrating the electrolyte with the cathode to achieve good interfacial contact often requires complex sintering processes. Herein, this work reports a solid electrolyte cathode assembly (SECA) which consists of a dense Li1.5Al0.5Ge1.5P3O12 (LAGP) layer and a carbon coated porous LAGP layer fabricated by facilely one-step sintering. As a result, Li–O2 batteries adopting the SECA showed a relatively high discharge capacity of 0.48 mAh cm−2 at 5 μA cm−2. Besides, the batteries could sustain six full cycles with a restricted capacity of 0.08 mAh cm−2 at 10 μA cm−2. It was found that the high capacity can be attributed to the high surface area of porous cathode structure.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
Journal of Physical Chemistry C
·
2014
·
IF 4.835
Wugang Fan,Xiangxin Guo,Dongdong Xiao,Lin Gu
Gold nanoparticles (AuNPs) anchored to vertically aligned carbon nanotubes (VACNTs) act as additional nucleation sites for the Li2O2 growth, leading to the decreased size while increased density of Li2O2 particles in process of discharge. Correspondingly, at the deep discharge to 2.0 V the batteries show increased specific capacity. Upon charge, the AuNPs exhibit promotion effect on the Li2O2 decomposition by improving the conduction property of the discharge-formed particles, rather than by imposing the conventional electrocatalytic effect on the oxygen evolution reaction. Moreover, the AuNPs show promotion effect on decomposition of carbonate species arising from the side reactions. These effects consequently lead to the reduced charge overpotentials and extended cycle operation of the batteries. The results here provide a new as well as clear picture on the role of incorporated AuNPs in the Li2O2 formation and decomposition, which would be helpful for better understanding and constructing of high-performance air cathodes.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2016
·
IF 5.31
Binbin Shao,Yufan Chen,Deli Wu,Chaomeng Dai,Yalei Zhang
Structural Fe(II/III) hydroxides on the shell of nano-zerovalent iron (nZVI) are reactive sites for As(III) adsorption. Well-controlled structural Fe(II) hydroxides (SFH) is prepared to serve for As(III) removal in present study. With oxygen As(III) removal by SFH occurred efficiently but the removal efficiency was greatly reduced under anoxic conditions. The mineral transformation from SFH to lepidocrocite probably contributed to the robust removal efficiency of As(III). It is found that Cu(II), Cr(VI) and NO 2 − in aqueous solution could act as oxidants and promote the mineral transformation of SFH. A more efficient As(III) removal was therefore observed without oxygen. The removal efficiency decreased in the order O 2 /SFH ≈ Cu(II)/SFH > Cr(VI)/SFH ≈ NO 2 − /SFH at near neutral pH. The removal efficiency was less dependent on the initial pH for O 2 /SFH and Cu(II)/SFH systems than Cr(VI)/SFH and NO 2 − /SFH systems. Distribution of As on solid phases was able to describe the removal mechanism of As(III), and the results showed that the mineral transformation promoted the precipitation process and inhibited outer-sphere complexation, thus leading to enhanced As removal. With Cu(II), Cr(VI) and NO 2 − , the generation of oxidants from SFH transformation drove As(III) oxidation, and contributed to total As removal.
研究领域:
环境科学
·
化学
✓ 已验证
DOI
高影响因子
SusMat
·
2021
·Vol. 1
·期 3
·448-457
·
IF 0
Zhaomin Chen,Xiaoqing Gu,Yutong Guo,Xin Wang,Mingwang Shao,Bin Dong,Zhenhui Kang
Electrochemical cell can overcome the inherent intermittence of the renewable energy sources, thus showing great potentials in applications ranging from electrical energy storage to future smart grid. However, the current electrochemical cells could not achieve the “total green” feature by fully utilizing the clean and abundant O 2 /H 2 O redox couples due to the enormous overpotentials for both oxygen reduction reaction (ORR) and oxygen release reaction (OER). Herein, we report a “total green” electrochemical composite film cell based on carbon dots (CDots), which can realize both ORR and OER in the acid environment. The in-air voltage generation (0.95 V, with a maximum power of 5.3 μW) relies on the multiple-electron-transfer redox chemical reaction between the two active components inside the composite film, that is, ORR/OER of CDots and the redox reaction of polyaniline (PANI) on the electrode and the resulting proton concentration gradient. Interestingly, the cell can be self-recovered at low load, recharged by adding H 2 O 2 , or electrocharged at high load. We anticipate that current study may open up new opportunities for designing and developing total-green energy storage and conversion systems for diverse applications.
研究领域:
材料科学
·
能源技术
·
环境科学
✓ 已验证
DOI
JOURNAL OF POWER SOURCES
·
2020
·
IF 8.247
Kang-Ning Gao,Hao-Ran Wang,Ming-Hui He,Yi-Qiu Li,Zhong-Hui Cui,Ya Mao,Tao Zhang
The development of solid-state lithium-oxygen batteries is currently limited primarily by the high solid-solid interfacial resistance and the lack of efficient assembly of electrolyte and electrode. In this work, noncovalent interactions between the cations of an ammonium ionic liquid and both solid electrolytes and carbon air cathodes are introduced. The ionic liquid-based electrolytes (ILE) are solidified on Li 6·40 La 3 Zr 1·40 Ta 0·60 O 12 (LLZTO) nanoparticles and gelated by multi-wall carbon nanotubes (MWCNTs), respectively, to construct LLZTO@ILE quasi-solid-state electrolyte (QSSE) and MWCNTs-LLZTO/ILE gel cathode (GC). The QSSE exhibits a high ionic conductivity of 1.71 × 10 −3 S cm −1 at 60 °C, high Li-ion transference number of 0.56, broad electrochemical window of ~4.8 V and good thermal stability . The GC shows outstanding compatibility with QSSE. Quasi-solid-state Li–O 2 batteries are assembled by integrating QSSE and GC films with a facile roll forming method, showing a low total interfacial resistance (~87 Ω cm 2 ), and excellent reversible cycles (70 cycles) with low charge overpotential (<0.44 V) and quite high electrical energy efficiency (>70%) at 60 °C and 200 mA g −1 . A 0.12 Ah pouch-type Li–O 2 battery was achieved by this method. These results suggest that the noncovalent interactions initiated by IL cations could be an effective approach to solve the solid-solid interface issue and achieve high discharge capacity in solid-state energy storage devices.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Xue Lu,Jingfang Li,Liye Liang,Guangming Li
Deep desulfurization with high-efficiency is imperia for environmental demands with increasing stringent standard of sulfur content in fuels. To develop high efficiency heterogeneous catalyst for aerobic oxidative desulfurization (AODS) of fuel, an Anderson-type CoMo 6 -2NH 2 (POM) as active site, which was considered to be very effective in catalyzing the activation of O 2 , was successfully anchored on the sub-stoichiometric ECOF as a carrier by Schiff-base condensation reaction between –NH 2 groups in CoMo 6 -2NH 2 and –CHO groups in ECOF. The anchoring of CoMo 6 -2NH 2 on ECOF by covalent bond resulted in the heterogenization of CoMo 6 -2NH 2 enabled CoMo 6 -2NH 2 @ECOF to be recyclable during the AODS process. When CoMo 6 -2NH 2 @ECOF was applied as catalyst for AODS of fuel with surfactant (OTAC) under O 2 , it exhibited excellent catalytic activity with almost 100 % removal rates under 95 °C for 6 h. Moreover, the catalyst can be recycled 7 times without significant loss of catalytic activity. Further, the structure-activity relationship was investigated and the reaction mechanism of AODS of fuel was verified by ESR, XPS analysis and selective quenching experiments.
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2026
·
IF 19.9
Yu Zhong,Xiaojuan Chen,Xinyang Zhang,Lei Qin
The capacity and lifespan of superoxide-based potassium–oxygen batteries (POBs) are limited by the failure of the potassium (K) anode due to oxygen crossover. The high-concentration potassium bis(trifluoromethanesulfonyl)imide (KTFSI)/dimethoxyethane recipe enables efficient anode passivation, but its high viscosity and elevated cost necessitate the use of a highly fluorinated ether co-solvent. In this study, we elucidate the indeterminate role of fluoroether in constructing the anode passivation layer. The fluoroether participates with TFSI − anions to form a robust solid electrolyte interphase (SEI) that effectively mitigates oxygen crossover. Moreover, the fluoroether shows a Janus effect that excessive addition triggers severe K corrosion, while an optimal amount leads to a desirable SEI on the K surface. This SEI acts both as an oxygen permeation barrier and as an efficient K + -conductive channel. With a more stable environment for the K anode, a POB utilizing the KTFSI-based electrolyte delivers over 200 cycles (above 800 h) with low round-trip overpotentials and high average coulombic efficiency (98.1%) as opposed to one using the potassium hexafluorophosphate-based electrolyte that fails early. Spectroscopic analyses and theoretical simulations were utilized to elucidate the molecular-scale interactions in the electrolyte components. This study provides fundamental insights and practical strategies for the development of long-life POBs.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF POLYMER SCIENCE
·
2026
·
IF 3.9
Jialong Yang,Guangqun Zhai
The effect of H 2 O 2 and H 2 O 2 -ascorbic acid (Vc) pairs on defunctionalization of 2-cyano-2-propyl dithiobenzoate (CPDB) and CPDB-mediated reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate (MMA) in dimethyl sulfoxide (DMSO) is investigated. The stability of CPDB toward H 2 O 2 is monitored by UV–vis absorption spectroscopy. CPDB is partially defunctionalized by H 2 O 2 alone and more seriously by H 2 O 2 -Vc pairs at 40°C, due to the oxidation by H 2 O 2 and the stepwise addition of DMSO-derived H 3 C· radicals. MMA greatly inhibits the defunctionalization of dithiobenzoate moieties, as both HO· and H 3 C· radicals incur oligomeric MMA-terminated alkyl radicals, which conserve the dithiobenzoate moieties of CPDB. H 2 O 2 -Vc-initiated CPDB-mediated RAFT polymerization is undertaken at 30°C and 40°C. Conversion is measured by gas chromatography, and molecular weight (MW) of PMMA is determined by gel-permeation chromatography. The processes manifest a moderately controlled fashion under optimal conditions. The products at low conversion display a multi-component composition, with high-MW PMMA consisting of 90% at least. MW of PMMA increases almost linearly with the yield and maintains a narrow distribution, but higher than the corresponding theoretical MW, owing to the partial defunctionalization of CPDB. Mass spectroscopy reveals that the irreversible termination of the intermediate radicals is the primary factor. Graphical H 2 O 2 initiated reversible addition-fragmentation chain transfer (RAFT) polymerization in dimethyl sulfoxide (DMSO) with 2-cyano-2-propyl dithiobenzoate (CPDB) as both the reducing agent and CTA. The defunctionalization of CPDB by H 2 O 2 in DMSO was observed, but methyl methacrylate significantly inhibited the defunctionalization. The CPDB-mediated RAFT polymerization was fulfilled with H 2 O 2 or H 2 O 2 -Vc pairs as the initiator. MS attributed the defunctionalization to the formation and the irreversible termination of lower-activity intermediate radicals.
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
·
2026
·
IF 12.2
Chang Ge,Yijie Yang,Qizheng Cai,Zheng Fang,Heng Dai,Man Tong,Songhu Yuan
Surface water–groundwater interaction zones are recognized as hotspots for reactive oxygen species (ROS) production. Entrapped gas bubbles formed due to water table fluctuations are important sinks and sources of dissolved oxygen (DO), whereas their influence on ROS production remains unknown. Here, we use column experiments to simulate surface water–groundwater interactions and quantitatively investigate the role of entrapped gas bubbles in the spatiotemporal distributions of DO and H2O2. During surface water recharge, gas bubbles act as O2 sinks, which uptake O2 from DO in the infiltrated surface water and thus restrict O2 penetration and the resultant H2O2 production. For subsequent groundwater discharge, the O2 stored in gas bubbles serves as a DO source for groundwater, which promotes H2O2 production. Cycles of groundwater discharge and surface water recharge experiments support the fact that the restriction and promotion effects induced by gas bubbles persist across recharge–discharge cycles. Reactive transport modeling reveals that the peak concentration and distribution area of H2O2 during surface water recharge decrease with the increase in the degree of gas saturation, but they increase during groundwater discharge. These findings highlight the previously overlooked dual roles of entrapped gas bubbles in ROS production and distribution under fluctuating hydrological regimes.
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）