CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Yong Liu,Mingjun Han,Jianye Liu,Yaling Huang,Yisi Liu,Wenzhang Li,Yang Liu,Jie Li
The practical implementation of Li-O 2 batteries remains constrained by three persistent challenges: sluggish oxygen redox kinetics, prohibitive costs of noble metal catalysts, and insufficient activity of non-precious alternatives. Herein, we present a novel ultralow Pt (0.25 wt%) single-atom loading Co 3 O 4 nanoneedle array catalyst (Pt 1 -Co 3 O 4 ) grown on carbon cloth via an ionic substitution strategy. This material functions as an advanced self-supporting cathode for aprotic Li-O 2 batteries. Benefiting from the surface self-reconstruction induced by Pt single-atom occupied the tetrahedral central sites of Co 3 O 4 , the electronic structure of Co 3 O 4 is modified, significantly enhancing the kinetics of both the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). As a result, the Pt 1 -Co 3 O 4 cathode demonstrates excellent cycling stability and a remarkably low discharge–charge overpotential of just 0.86 V. Furthermore, the Li-O 2 battery with this cathode exhibits a high discharge-specific capacity (8.20mAh cm −2 ) and long cycling life (220 cycles, >1100 h at 0.1 mA cm −2 ), outperforming all reported Co 3 O 4 -based ORR/OER catalysts, as well as many non-noble metal catalysts, even those with significant noble metal loading. Crucially, the thin-film-like layers of discharge product Li 2 O 2 are uniformly dispersed on the Pt 1 -Co 3 O 4 nanoneedles. This reduces the adsorption energy between LiO 2 /Li 2 O 2 and Pt 1 -Co 3 O 4 compared to Co 3 O 4 , ensuring good structural stability during discharge/charge cycles and facilitating the decomposition of discharge products during recharge, thus reducing overvoltage and enhancing battery efficiency. These findings position Pt 1 -Co 3 O 4 as a promising catalyst for Li-O 2 batteries and open new avenues for the development of oxide-based single-atom catalysis.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
LANGMUIR
·
2025
·
IF 3.9
Yu-Le Wang,Cong Wang,Song-Hai Wu,Yong Liu,Xu Han
Although spontaneous H2O2 accumulation by sacrificial oxidation of metal disulfides (FeS2, NiS2, etc.) under oxic conditions without external electrical/photonic input has been observed, the mechanistic understanding of HCO3– on the production of H2O2 is still not clear. In this study, HCO3– apparently accelerates the production of H2O2 on NiS2, and the produced H2O2 increases from 53.85 to 90.12 μM with increasing concentrations of HCO3– from 0 to 0.5 M at pH 9.0. Electrochemical analyses indicate that HCO3– effectively mediates the 2e reduction of O2 to H2O2 on the surface of NiS2. EPR and Raman analyses rule out the primary contributions of soluble •OH and O2•– to the production of H2O2 and reveal the presence of both ≡Ni–OO• superoxo and ≡Ni–OOH peroxo on NiS2, which are important precursors for H2O2. The presence of CO3•– also indicates that HCO3– is an important H-donor during the reduction of O2 to H2O2. DFT calculations further reveal that it is thermodynamically more favorable for ≡Ni–OO• and ≡Ni–OOH to abstract H from HCO3– than from H2O to produce H2O2, confirming that HCO3– is a better H-donor than H2O to produce H2O2 via the H-abstraction pathway. This study provides insight into the importance of HCO3– on spontaneous H2O2 accumulation by sacrificial oxidation of NiS2 under oxic conditions without external electrical/photonic input.
✓ 已验证
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2016
·Vol. 5
·期 2
·544-553
·
IF 8.262
Qin Zhao,Caixia Wu,Lina Cong,Yuhang Zhang,Guiru Sun,Haiming Xie,Liqun Sun,Jia Liu
Controlling the geometric morphology and distributive location of discharge products play an important role in the reversibility and efficiency of Li–O2 batteries. This work presents novel Co2CrO4 nanospheres (CCO) prepared via a facile method, which are applied as the electrocatalysts for Li–O2 batteries. The as-prepared CCO was characterized by XRD, XPS, SEM, TEM, BET, and TG measurements. The CCO exhibited a yolk–shell microstructure, which could facilitate fast Li+ and O2 diffusion as well as possessing enough space for the discharge product deposition. In comparison to the performance of the cell without catalyst, the overpotential of the cell with CCO was apparently reduced and the cyclability significantly enhanced. Based on the experimental results and DFT calculations, direct evidence of the CCO employment being linked to the Li2O2 morphology was provided. In addition, a catalytic mechanism was proposed. Furthermore, fundamental information about the key factors and steps involved in the Li2O2 formation and decomposition was revealed. We expect that this study gives insight into the development of electrocatalysts, the selection of O2 electrode materials, and the design of O2 electrodes for Li–O2 batteries, as well as advancing our understanding of the catalytic mechanism.
研究领域:
材料科学
·
电化学
·
能源存储与转换
✓ 已验证
DOI
高影响因子
Energy Storage Materials
·
2022
·
IF 20.831
Xuecheng Cao,Chaohui Wei,Xiangjun Zheng,Kai Zeng,Xin Chen,Mark H. Rummeli,Peter Strasser,Ruizhi Yang
Lithium–oxygen (Li–O 2 ) batteries have attracted tremendous attention due to their high specific energy density . However, their sluggish conversion kinetics and detrimental parasitic reactions would deteriorate the lifespan of batteries. Herein, a combined density functional theory (DFT) calculation and experimental approach is carried out to design an efficient cathode electrocatalyst for Li–O 2 batteries. A self-supporting film of Ru clusters anchored on Magnéli phase Ti 4 O 7 enriched with oxygen vacancy (Ru/Ti 4 O 7 ) is fabricated upon electrospinning and carbothermal reduction. In such a synergistic configuration of Ru/Ti 4 O 7 hybrid film, the strong metal-support interaction (SMSI) between Ru and Ti 4 O 7 can improve the charge transfer at the interface and enhance the adsorption energy of intermediates, accelerating the reaction kinetics of the formation/decomposition of Li 2 O 2 . Benefitting from this SMSI, the electrochemical stability of Ru/Ti 4 O 7 over cycling is also enhanced. As a result, as-prepared Ru/Ti 4 O 7 cathodes could realize excellent electrochemical performance , including high specific capacity (11000 mAh g –1 ), low discharge/charge polarization (0.36 V), long lifespan (> 100 cycles) and superior rate capability. Furthermore, a flexible Li–O 2 pouch cell, constructed with as-fabricated Ru/Ti 4 O 7 film cathode, lithium foil anode and GPE , can exert an impressive areal capacity of 5 mAh cm –2 with a low voltage gap of 0.82 V in ambient air. This work suggests that the activity of catalysts can be significantly enhanced with interfacial modification, offering an efficient approach for rational designing of electrocatalysts for use in Li–air batteries and beyond.
研究领域:
材料科学
·
能源科学
✓ 已验证
DOI
高影响因子
ChemSusChem
·
2024
·
IF 7.5
Dan Li,Qian Chen,Rui Li,Yaolin Hou,Yulong Liu,Haiming Xie,Jia Liu,Jiefang Zhu
Graphical The incorporation of the polyionic liquid additive [PBVIm]-TFSI in LiI-mediated Li-O 2 batteries enables the in situ formation of a protective layer on the Li anode. [PBVIm] + cations migrate to the Li anode, forming a cationic shield that promotes uniform Li + deposition. A [PBVIm][TFSI]-containing cell demonstrates a considerable reversibility and cycling stability. Redox mediators (RMs) have shown promise in enhancing Li-O 2 battery cycling stability by reducing overpotential. However, their application is hindered by the shuttle effect, leading to RM loss and Li anode corrosion. Here, we introduce a polyionic liquid, poly (1-Butyl-3-vinylimidazolium bis(trifluoromethanesulfonylimine)) ([PBVIm]-TFSI) as an additive, showcasing a novel Li anode protection strategy for LiI-mediated Li-O 2 batteries. [PBVIm] + cations migrate to the Li anode, forming a protective cationic shield that promotes uniform Li + deposition. The addition of [PBVIm]-TFSI enhances the cycling stability, achieving 105 cycles at 200 mA⋅g −1 , compared to the cell with LiI which exhibited 38 cycles under the same conditions. Synchrotron X-ray tomography reveals the evolution of this protective layer, providing insights into its formation mechanism, in conjunction with XPS analysis. Our findings offer a new approach to Li anode protection in Li-O 2 batteries, emphasizing the critical role of interfacial engineering for battery performance.
研究领域:
材料科学
·
电化学
·
能源存储
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
shuailong Song,Zhinan Wu,Tong Zhou,Yunxia Wen,Wei Cao,Han Lin,Xiaohua Lu,Tuo Ji,Jiahua Zhu
The major challenge that solid amine sorbents face in practical large-scale applications is their susceptibility to degradation under humid and oxygen-containing conditions. This study developed a superhydrophobic alkyl-silica by co-hydrolyzing alkyl-silane and tetraethyl orthosilicate and then immobilizing polyethyleneimine as a CO2 sorbent. By adjusting the chain length and density, the surface of the alkyl-silica has abundant alkyl chains, and the PEI molecules are intercalated into the surface alkyl layer. These alkyl chains effectively block the contact of O2 and H2O with the amine group, thereby selectively allowing the adsorption/desorption of CO2 molecules through the alkyl layer. The results showed that the working capacity of PEI/alkyl-silica was maintained at 86% by oxidation treatment and 85% by rinsing treatment, respectively, exhibiting excellent stability compared to unprotected PEI/SiO2. Meanwhile, the alkyl chain due to the steric hindrance effect weakens the interaction between CO2 and amine and does not reduce its original working capacity. The energy consumption of PEI/alkyl-silica during regeneration was lowered to 1.24 GJ·t-1-CO2. This interfacial building concept provides a new path for designing a long-term stable amine sorbent for cost-effective CO2 capture by avoiding the contact of O2 and H2O with the amine.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Changshun Deng,Xiaorong Zhu,Jun Yao,Yibo Wang,Chenyang Shen,Bingqing Ge,Chaoxiang Li,Nianhua Xue,Luming Peng,Xuefeng Guo,Yan Zhu,Yafei Li,Weiping Ding
The direct oxidation of toluene by O 2 to benzaldehyde with high efficiency is a bright route for the green production of benzaldehyde but still a significant challenge. In this study, we develop a ligand modification strategy by bonding organophosphonic acid (OPA) to VTiO x /γ-Al 2 O 3 to restructure its interface microenvironment for enhancement of toluene oxidation to benzaldehyde. The as-prepared catalyst exhibits excellent selectivity over 99 % under mild conditions. Results of comprehensive characterizations and calculations reveal that the OPA bonding in bidentate with the V 6-coordinated species causes noticeable phase reconstruction between VO x and TiO 2 , thereby generating nearby new reactive oxygen species, which is responsible for the conversion of toluene to benzaldehyde at temperatures as low as ∼50 °C, much lower than that over VO x /TiO 2 (>130°C). The interface microdomain around the bonding site of OPA helps to significantly weaken the methyl C H bond of toluene molecule in reaction manifested as the significant decrease in apparent activation energy. Hence, the current work reveals a novel mechanism of the typical catalyst VO x /TiO 2 under OPA bonding, which is useful to solve the classic difficult reaction of toluene to benzaldehyde by O 2 oxidation.
研究领域:
催化化学
·
绿色化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Jiaming Wang,Feifei Kang,Yifei Chen,Xiujuan Zhang,Xiaobin Jiang,Gaohong He,Xuehua Ruan
Artificial lung membranes are the heart for extracorporeal oxygenation. Hereinto, the nonporous PDMS-based membranes have excellent biocompatibility, and also isolation ability to both blood and harmful matters. Nevertheless, their CO 2 /O 2 selectivity, in the conventional cases using pure-oxygen sweeping stream, is not enough to accomplish sufficient CO 2 removal in balance with O 2 addition. In this work, the oxygenation mode using oxygen-enriched stream, faithfully based on the permeation mechanism, is established to overcome this bottleneck. To neutralize the negative impacts caused by lowering oxygen content and its partial pressure, PDMS-based composite membranes with ultra-thin selective layer to enhance mass transfer have been fabricated successfully. The experiments manifest that the selective layer, on the basic condition that the composite structure is stable enough to make surface modification and realistic utilization, is decreased to 376 nm on the porous substrates. O 2 and CO 2 permeation rates through the ultimate membrane samples have been enhanced to 502 GPU and 4117 GPU, respectively. In this instance, the essential oxygenation could be sustained with O 2 partial pressure less than 446 mmHg in the sweeping stream. The minimum membrane area for a common treatment case is 0.05 square meters. Once the membrane area is increased to 0.18 square meters, the sterile air after purification could be directly used for oxygenation. In comparison to the oxygenation devices being used currently, membrane area can be saved by about 90 %, which is highly significant to reduce the injuring influence on blood cells. All in all, the artificial lung membranes with ultra-thin PDMS coating layer have promising future in realistic utilization.
研究领域:
生物医学工程
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
·
2024
·
IF 11.2
Shuang Zhou,Da Wen,Wei Zhong,Jianjun Zhang,Yaorong Su,Aiyun Meng
The effective adsorption of oxygen (O 2 ) molecules over photocatalysts is a critical step in promoting the performance of photocatalytic H 2 O 2 production. However, g-C 3 N 4 usually features a Yeager-type (side-on) adsorption configuration of O 2 molecules, which causes the breaking of O–O bonds and severely hinders the H 2 O 2 production activity. Herein, we synthesized an oxygen-vacancy-rich TiO 2– x /g-C 3 N 4 step-scheme (S-scheme) heterojunction to regulate the oxygen adsorption configuration and improve the 2e – ORR selectivity of H 2 O 2 production. In-situ X-ray photoelectron spectroscopy (in-situ XPS) and density functional theory (DFT) calculations reveal that the S-scheme heterojunction is formed between TiO 2– x and g-C 3 N 4 . The difference between their Fermi levels leads to the electron flow from g-C 3 N 4 to TiO 2– x , which increases the electron-deficient sites in g-C 3 N 4 . As a result, the cleavage of O–O bonds on the surface of g-C 3 N 4 is avoided and the oxygen adsorption configuration is tuned from Yeager-type to Pauling-type (end-on). Consequently, the photocatalytic H 2 O 2 production rate is dramatically improved to 1780.3 μmol h –1 , which is about 5 times higher than that of pristine g-C 3 N 4 . This work paves a new way to tailor the oxygen adsorption configuration by rationally designing S-scheme heterojunction photocatalysts.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
TALANTA
·
2024
·
IF 5.6
Yucheng Zhou,Chaoyan Zhang,Jiyang Liu,Yiping Mou
Sensitive detection of tumor biomarkers is of great significance for early cancer diagnosis, treatment evaluation, and recurrence monitoring. Development of convenient electrochemiluminescence (ECL) immunosensor using dissolved oxygen (O 2 ) as an endogenous co-reactant of luminol combined with efficient nanocatalysts to boost ECL signal in neutral media is highly desirable. Herein, sensitive detection of tumor biomarker using ECL of luminal-O 2 enhanced by confinement of nitrogen-doped graphene quantum dots (N-GQDs) and platinum nanoparticles (PtNPs) on nanochannel array was demonstrated. A high-density nanochannel array-modified electrode was achieved by rapidly growing an amino-functionalized vertically-ordered mesoporous silica film (NH 2 -VMSF) on the inexpensive and readily available indium tin oxide (ITO) electrode. Through simple electrodeposition, N-GQDs were confined and PtNPs were in-situ synthesized in nanochannels of NH 2 -VMSF. These confined nanocomposites catalyzed the electroreduction of O 2 at negative potentials to generate a large amount of reactive oxygen species (ROS) and facilitated luminol oxidation, enhancing the ECL signal of luminol by 25 times. Two immunosensors were fabricated after covalent immobilization of the recognition antibody of carbohydrate antigen 199 (CA199) or carbohydrate antigen 125 (CA125) on the outer surface of the NH 2 -VMSF and blocking of non-specific sites. When tumor biomarkers bind to the corresponding antibodies on the recognition interface, the formed immunocomplex hindered the diffusion of luminol to the underlying electrode, resulting in a decrease in the ECL signal and sensitive detection of tumor biomarker. The constructed CA199 immunosensor exhibited a linear detection range for CA199 from 0.5 mU mL −1 to 50 U mL −1 , with a detection limit (DL) of 0.03 mU mL −1 . For CA125 detection, linear detection ranged from 0.5 mU mL −1 to 500 U mL −1 , with a DL of 0.005 mU mL −1 . The fabricated immunosensors demonstrated good selectivity and high reproducibility. This study provides great potential for the development of efficient luminol ECL systems in neutral media and expands the biological application in sensitive detection of tumor biomarker.
研究领域:
生物医学工程
·
分析化学
·
癌症诊断
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SCIENCE OF THE TOTAL ENVIRONMENT
·
2021
·
IF 7.963
Ran Yang,Jun Cai,Hu Yang
Zero-valent aluminum (ZVAl) is a promising reductant because of its relatively low redox potential , which can efficiently activate molecular oxygen to generate reactive oxygen species . However, its long-term performance is limited by the intrinsic dense oxide layer and the passivation effect of the accumulative Al-(hydr)oxide on its surface during the reaction. In this study, four clay minerals with different compositions were mixed with ZVAl by ball milling to obtain four composites of ZVAl and clay (ZVAl-Clay), which were used to degrade a high concentration of 4-chlorophenol (4-CP) under ambient conditions. The oxidation efficiencies of different ZVAl-Clays were strongly relevant to Fe contained in the clay minerals. The Fe-free ZVAl-Clay presented poor oxidation performance, whereas the reaction efficiencies of those ZVAl composites with Fe-bearing clays exhibited varying degrees of improvement. In comparison with the original ZVAl, the highest oxidation rate increased by 23 times, the maximum increased OH production was approximately 8 times, and the corresponding mineralization efficiency improved by 38.7%. However, the levels of improved oxidation performance of various ZVAl-Clays were not positively correlated with their actual total Fe contents, and their degradation efficiencies might also be affected by other physical and/or chemical properties of different clays. The synergistic mechanism revealed by various characterizations was that electron transfer might occur from ZVAl to the structural Fe(III) of the clay through the basal plane or edge of clays triggered by ball milling. Thus, the partially produced Fe(II) on the clay surface promoted the Fenton-like reaction to decompose H 2 O 2 into OH for efficient oxidation of 4-CP. In short, the ZVAl composites with Fe-bearing clays deserved further exploration as potential materials for efficient degradation of organic matters in wastewater samples.
研究领域:
环境科学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
JOURNAL OF THE ELECTROCHEMICAL SOCIETY
·
2017
·Vol. 164
·期 6
·A1321
·
IF 3.259
Chaolumen Wu,Taoran Li,Chenbo Liao,Qingkai Xu,Yuancheng Cao,Lei Li,Jun Yang
Triethylene glycol dimethyl ether (G3) is evaluated as an electrolyte solvent for non-aqueous lithium-oxygen (Li-O2) batteries. A liquid electrolyte of 1 M LiTFSI in G3 shows lower viscosity, higher oxygen solubility and diffusion, higher ionic conductivity and lithium ionic transference number compared to the conventional liquid electrolyte of 1 M LiTFSI in tetraethylene glycol dimethyl ether (G4). Then the Li-O2 battery using the G3-based electrolyte shows better cycling stability and higher rate capability compared to the battery using the G4-based electrolyte. At a higher current density of 2.5 A gcarbon−1, the discharge capacity of the battery using the G3-based electrolyte is about 1472 mAh gcarbon−1, which is about four times higher than that of the battery using the G4-based electrolyte. At current density of 1 A gcarbon−1 with a fixed capacity of 1000 mAh gcarbon−1, the battery using the G3-based electrolyte can be operated stably for 80 cycles, while only 20 cycles are achieved by using the G4-based electrolyte. Therefore, we think the G3-based electrolyte could be a proper alternative electrolyte to the conventional G4-based electrolyte for the development of Li-O2 batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）