ELECTROCHIMICA ACTA
·
2023
·
IF 6.6
Congcong Dang,Pu Feng,Sixian He,Liancheng Zhao,Aidang Shan,Ming Li,Lingti Kong,Liming Gao
The design of ultra-stable cathode materials of Li-O 2 batteries with excellent catalytic performance is very important and desirable. However, some problems such as sluggish electrochemical reaction kinetics and unwanted side reactions still remain challenging. Carbon materials own hierarchical porous structure which facilitates mass transport and accommodates discharge products but are not stable enough as cathode of Li-O 2 batteries. Here in, we fabricated a unique NiCo bimetallic phosphide combined with carbon nanotube heterostructure (abbreviated as NiCoP/CNT) by hydrothermal method. Density functional theory (abbreviated as DFT) calculation demonstrates that bimetallic phosphide NiCoP/CNT delivered much better electrical conductivity, greater adsorption to reactants, and more electron transfer with discharge products Li 2 O 2 , compared to monometallic phosphides CoP and Ni 2 P. Therefore, NiCoP/CNT based cathode displayed low overpotential of 0.87 V at current of 100 mA g −1 with a fixed specific capacity of 1000 mAh g −1 and run steadily over 150 cycles under high current of 500 mA g −1 with a fixed specific capacity of 1000 mAh g −1 . Furthermore, Ex-situ X-ray Photoelectron Spectroscopy and in-situ differential electrochemical mass spectroscopy proved the existence of intermediate products Li 2-x O 2 . This approach provides a reference for designing and synthesis of bimetallic cathode in Li-O 2 batteries.
研究领域:
材料科学
·
电化学
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DOI
高影响因子
ELECTROCHIMICA ACTA
·
2016
·
IF 4.803
Jingpeng Wang,Chunyu Du,Xing Xu,Xiaoshu He,Geping Yin,Yulin Ma,Pengjian Zuo,Xinqun Cheng,Yunzhi Gao
A facile high-temperature solid phase approach is employed to coat lithium phosphorus oxynitride (LiPON) layer on the concentration gradient Li[Ni 0.73 Co 0.12 Mn 0.15 ]O 2 material with Ni-rich core and Ni-poor surface. X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy demonstrate that LiPON forms an even coating with ∼4 nm of thickness on the surface without destroying the bulk structure of Li[Ni 0.73 Co 0.12 Mn 0.15 ]O 2 material. The LiPON-coated concentration gradient Li[Ni 0.73 Co 0.12 Mn 0.15 ]O 2 material exhibits a capacity retention of 87.3% at 25 °C after 1000 cycles and 89.9% at 55 °C after 250 cycles, which is 36.1% and 17.2% higher than that of pristine Li[Ni 0.73 Co 0.12 Mn 0.15 ]O 2 material, respectively, under the same operating conditions. This significantly improved cycling performance is ascribed to the noncrystalline LiPON layer on the surface, which provides a reliable interface protection. The LiPON coating is an effective approach to enhancing the electrochemical performance of electrode materials for lithium ion batteries.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Shidong Song,Dequan Zhang,Yanli Ruan,Limei Yu,Yongqiang Xu,Joykumar Thokchom,Donghai Mei
Heightened attention for solid-state Li–O2 batteries (SSLOBs) exists due to their improved safety, wider electrochemical window, and high energy density in addition to the solid electrolyte’s innate capability of suppressing Li dendrite penetration and shielding the Li metal anode from oxygen, CO2, and moisture in the air, in comparison with the conventional Li–O2 batteries using liquid organic electrolytes. Herein, a cathode supported quasi-SSLOB with an integrated composite polymer-based architecture (ICPA) is developed with reduced interfacial resistance, extended triple-phase boundaries (TPBs) for Li–O2 reactions, and a thin film solid-state electrolyte. The Li–O2 cell with ICPA (denoted as ICPA cell) exhibits a lower charge transfer impedance than its counterpart with the same composite polymer electrolyte (CPE) but a nonintegrated structure (termed the CPE cell). The former shows reduced interfacial impedance between electrolyte and cathode and increased TPBs. Furthermore, the ICPA cell delivers higher discharge capacity, lesser capacity decay, and significantly lower impedance rise after cycles than the CPE cell, ascribed to the continuous Li-ion transport in ICPA and the resulting more efficient discharge and charge processes. Under a limited capacity cycling protocol of 300 mAh g–1, the ICPA cell achieves excellent reversibility for 78 cycles, remarkably surpassing the CPE cell which only performs 44 cycles in addition to showing half of the after-cycle impedance compared to that for the CPE cell. Nonetheless, the same composite polymer electrolyte used for both CPE- and ICPA-based cells demonstrates excellent stability toward Li metal after long-term cycling. These findings manifest that the design and application of cathode supported SSLOB with ICPA can be a promising approach to achieve high-performance Li–O2 batteries.
研究领域:
材料科学
·
电化学
·
能源存储技术
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2018
·
IF 11.698
Anye Shi,Huihui Li,Shu Yin,Zaili Hou,Jiayue Rong,Jiachi Zhang,Yuhua Wang
Cs x WO 3 nanorods can be used to sensitize the single layer g-C 3 N 4 , where full spectrum light harvesting excited electrons to drive the photocatalytic reduction of N 2 into NH 3 . Under UV light, both water splitting and solar ammonia synthesis reaction exhibit high activity. However, selectivity towards ammonia over hydrogen is realized under NIR irradiation. With the control of methanol, O 2 can directly decide the NH 3 or H 2 evolution on photocatalyst. The origin is the strong capture of O 2 with the electrons from the photocatalyst under light irradiation to yield the oxygen active species, which transfer electrons subsequently with help of methanol to generate NH 3 . However, H 2 production will be suppressed by O 2 . And with its sacrifice, methanol preserves the produced NH 3 from oxidation. The O 2 -sacrificial agent mediated NH 3 evolution reaction found here provides insights in the promotion role of them in other catalysis.
研究领域:
材料科学
·
环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
ENERGY & FUELS
·
2020
·
IF 3.421
Qiongqiong Jiang,Yali Cao,Xiangyu Liu,Hao Zhang,Hui Hong,Hongguang Jin
Chemical looping combustion (CLC) can achieve the benefits of efficient conversion of hydrocarbon fuels and zero-energy CO2 capture using oxygen carriers (OCs) with facilitated oxygen transport properties. The current study details the use of Cu- and Ca-doped lanthanum nickel perovskite-type materials as the OC in CLC processes. By incorporation of lanthanum nickel oxide with copper and calcium, the oxygen storage capacity and average transport rate of La1–yCayCuxNi1–xO3 are up to 7.8 wt % and 0.82 wt % min–1, respectively, during the methane CLC process at 400 °C, whereas undoped LaNiO3 cannot react with methane at a low temperature. Simultaneously, substituted lanthanum nickel oxides can decrease the oxygen transport temperature by about 70 °C compared to undoped lanthanum nickel oxide. X-ray diffraction, Brunauer–Emmett–Teller, and scanning electron microscopy of the samples were characterized in terms of particle properties and morphology to unveil the rational reasons of the high oxygen transport at lower temperatures. The enhancement of the specific surface area and stable porous morphology in La1–yCayCuxNi1–xO3 can both facilitate the oxygen transport in CLC processes. Experiments were executed to investigate the reactivity of the redox materials on the standpoints of oxygen capacity, stability, and regenerability. Hydrogen and methane as the fuels are both considered in this study. La1–yCayCuxNi1–xO3 showed favorable reactivity and stability in the successive redox cycles at low temperatures. These experimental results indicate that La1–yCayCuxNi1–xO3 can facilitate O2– transport and have the potential to be used as the promising OC for low-temperature CLC processes.
研究领域:
能源化学
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材料科学
·
化学工程
·
环境科学
·
催化化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Akkammagari Putta Rangappa,Wei Xiong,Xinxin Lu,Guohan Sun,Yixuan Liu,Jiangdong Dai,Jun Zhao
CTAB assisted synthesis of FeS 2 allows precise control over surface sulfur vacancies. • Surface-modified FeS 2 boosts O 2 activation and enhances reactive oxygen species (ROS) population. • Vs-rich FeS 2 lowers HMF conversion barrier, giving 15.73 fold higher DFF yield than pristine FeS 2 . • Synergy of Vs and Fe redox cycling in FeS 2 accelerates charge transfer and surface reactivity. • Tuning defects and redox states in FeS 2 enable sustainable and versatile photocatalysis. The photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF) using molecular oxygen (O 2 ) as the oxidant offers a sustainable route for biomass valorization, yet is limited by inefficient O 2 adsorption and activation on conventional photocatalysts. Herein, we report a Cetrimonium bromide (CTAB) assisted synthesis of iron pyrite (FeS 2 ) with engineered surface sulfur vacancies (Vs) that enable simultaneous activation of O 2 and HMF under solar light. Introduction of Vs increases the catalyst’s specific surface area and modulates the local electronic structure, particularly tuning the Fe 2+ /Fe 3+ redox landscape. These defect sites act synergistically, where Fe 2+ sites act as preferred O 2 adsorption centers, while adjacent Vs promote electron localization and transfer to adsorbed O 2 , thereby facilitating its activation through the oxidation of Fe 2+ to Fe 3+ . Concurrently, the modulated Fe redox states enable efficient HMF adsorption and oxidation through interaction with the activated O 2 species (•O 2 – and 1 O 2 ). This dual activation mechanism, driven by vacancy engineering and Fe redox dynamics, enhances charge transfer kinetics and surface reactivity, leading to a 15.7-fold increase in DFF production compared to prismatic FeS 2 . Our findings emphasize the critical role of Vs and Fe 2+ /Fe 3+ redox interplay in organizing simultaneous O 2 activation and HMF oxidation, advancing the rational design of efficient photocatalysts for biomass-derived chemical production. Download: Download high-res image (117KB) Download: Download full-size image
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DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2026
·Vol. 14
·期 35
·16045-16056
·
IF 7.6
Ge Xiao,Wu Xinyi,Liu Xinya,Zheng Xiyang,Xu Jinze,Tian Li-jiao,Wang Wei,Wang Xiaozhi
Spin state strongly governs the pathway selectivity of photocatalytic oxygen reduction, dictating whether the reaction proceeds via the desired two electron (2e – ) route to H 2 O 2 or the competing four electron (4e – ) pathway. Herein, this work reports a ligand-field symmetry-breaking strategy that enables controlled spin state switching, thereby steering the oxygen reduction pathway toward selective two electron H 2 O 2 production. Specifically, symmetry breaking creates an asymmetric equatorial ligand field, triggering a deterministic spin state transition from intermediate spin to high spin on the Mn site. The resulting high-spin configuration features delocalized d-states and a downshifted d-band center, which collectively weaken *OOH adsorption to suppress premature O–O bond cleavage while preserving efficient O 2 activation through spin polarized electron transfer. As a result, the optimized high spin catalyst delivers an exceptional H 2 O 2 production rate of 5025 μmol·g –1 ·h –1 under simulated sunlight, representing a 2.3-fold enhancement over its intermediate spin (IS) counterpart. Furthermore, its activity is maintained under natural sunlight in ambient air, achieving a H 2 O 2 production rate of 2662 μmol·g –1 ·h –1 . This work establishes ligand field symmetry breaking as a precise and generalizable paradigm for spin state engineering in single atom catalysis, offering a direct route to overcome the selectivity efficiency compromise in photosynthesis of H 2 O 2 .
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产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Yingdong Hao,Yonghui Zhao,Jun Ma,Xinru Han,Yingxiao Wang,Pengyu Chen,Deng Hu,Yuefeng Liu,Wei Wei,Nannan Sun
Photocatalytic oxidation of methane (CH4) to high value-added liquid oxygenates with oxygen (O2) as an oxidant has long been a promising process. In addition to the activation of CH4, the selective reduction of O2 to hydroperoxyl (·OOH) is also a crucial factor in determining the efficiency and selectivity of the overall reaction. In thermal catalysis, strong interactions between oxygen vacancies (OVs) on the catalyst surface and O2 are widely adopted as a means of enhancing O2 activation. However, reports of this phenomenon are limited in photocatalysis; this is attributable to the fact that the reduction of O2 is dependent upon its reaction with photogenerated electrons (e–). For the majority of photocatalysts, the transfer of e– to metal cocatalysts results in the spatial separation of e– from OVs. Therefore, the intrinsic affinity between OVs and O2 is not fully exploited. In this study, we discovered that H2 treatment at elevated temperatures on ZIF-8-derived ZnO led to the formation of an OV-enriched amorphous layer on the surface. After the introduction of the Ag cocatalyst, the as-prepared Agx-OVs/ZnO exhibited an unconventional carrier transfer direction, whereby photogenerated e– and holes (h+) are transferred to OVs and Ag, respectively. As a result, the preferential O2 adsorption and activation sites can be spatially combined together on the OVs and thus drive the reduction of O2 to realize efficient and directed generation of ·OOH. In parallel, the transfer of h+ to the Ag sites weakens its oxidation capability and avoids overoxidation while ensuring CH4 activation. The optimized defect-rich Ag0.5-OVs/ZnO-z photocatalyst reaches a high liquid oxygenate yield of 10148 μmol gcat–1 h–1 with 95% selectivity and a high TOF of 2.4 × 106 μmol gAg–1 h–1. This work sheds new light on the design of photocatalytic CH4 oxidation catalysts via manipulation of carrier transfer direction.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACTA PHYSICO-CHIMICA SINICA
·
2014
·Vol. 30
·期 1
·150-156
·
IF 0.886
YANG Bing-Jian,WANG Hong,Li Lei,HUANG Bo-Wen,LIAO Xiao-Zhen,HE Yu-Shi,MA Zi-Feng
The development of low-cost and effective electrocatalysts for air electrodes is critical for practical applications of lithium/oxygen batteries. In the present work, phenanthroline (phen) was used as a ligand to prepare a Co(phen)2 complex. The Co(phen)2 complex
was coated on BP2000 and then heat treated at 600, 700, 800, and 900 , to obtain carbon-supported Co-N (Co-N/C) catalysts. The catalytic activities in oxygen reduction reaction/oxygen evolution reaction (ORR/OER) of the prepared catalysts were measured and compared with those of a typical
carbon-supported cobalt tetramethoxyphenylporphyrin (CoTMPP/C) catalyst. The influence of the calcination temperature on the composition and structure of the Co-N/C catalysts was investigated. Electrochemical tests showed that the Co-N/C catalysts prepared at 700 and 800 gave better performances,
comparable to that of the CoTMPP/C catalyst. The superior electrochemical performance of the prepared Co-N/C catalysts and the low cost of the phenanthroline chelating agent make Co-N/C a promising cheap catalyst for lithium/oxygen batteries.
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
BIOMATERIALS
·
2018
·
IF 8.806
Shutao Gao,Pengli Zheng,Zhenhua Li,Xiaochen Feng,Weixiao Yan,Shizhu Chen,Weisheng Guo,Dandan Liu,Xinjian Yang,Shuxiang Wang,Xing-Jie Liang,Jinchao Zhang
Improving the supply of O 2 and the circulation lifetime of photosensitizers for photodynamic therapy (PDT) in vivo would be a promising approach to eliminate hypoxic tumors. Herein, by taking advantage of the significant gas-adsorption capability of metal-organic frameworks (MOFs), a biomimetic O 2 -evolving photodynamic therapy (PDT) nanoplatform with long circulating properties was fabricated. Zirconium (IV)-based MOF (UiO-66) was used as a vehicle for O 2 storing, then conjugated with indocyanine green (ICG) by coordination reaction, and further coated with red blood cell (RBC) membranes. Upon 808 nm laser irradiation , the initial singlet oxygen ( 1 O 2 ) generated by ICG would decompose RBC membranes. At the same time, The photothermal property of ICG could facilitate the burst release of O 2 from UiO-66. Subsequently, the generated O 2 could significantly improve the PDT effects on hypoxic tumor. Owing to the advantages of long circulation and O 2 self-sufficient, the designed nanotherapeutic agent can improve the efficiency of treatment against hypoxia tumor via PDT. Hence, this study presents a new paradigm for co-delivery of O 2 and photosensitizers, and provides a new avenue to eliminate hypoxic tumors.
研究领域:
生物医学工程
·
纳米技术
·
癌症治疗
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Yue Tang,Xiaolin Pi,Huiying Li,Xueni Zhang,Lijun Luo,Fengzhi Jiang
This study presents the synthesis of highly active BiPO 4 /AgI/BC composite photocatalysts via a green, simple, and low-cost ambient temperature precipitation method. The electron transfer rate and visible-light responsiveness can be effectively enhanced by utilizing BiPO 4 compounded with the semiconductor AgI, which has a narrow bandgap and good visible-light responsiveness. Additionally, the introduction of biocarbon (BC) enhances the absorption and separation of photogenerated electrons and holes under visible light. Notably, the synthesized BP-AgI 0.6 -BC 5 % could remove 99.16 % and 99.7 % of EE2 and E2, respectively, at a concentration of 3 mg/L after 40 min of light exposure. The capture experiments and electron paramagnetic resonance spectroscopy reveal that the main active substance in the system is ·O 2 - , with BC playing a crucial role in enhancing the ·O 2 - concentration in the system. The findings from phytotoxicity and antimicrobial tests reveal that BP-AgI 0.6 -BC 5 % can efficiently degrade pollutants, producing degradation products that are substantially less toxic than the original pollutants. Moreover, it can remove more than 99.99 % of E. coli under both dark and light conditions, demonstrating excellent antimicrobial performance. Additionally, the photocatalytic mechanism and degradation pathway were examined in this study. Notably, the composite photocatalysts synthesized in this study achieved efficient degradation of EE2 and E2 under visible light conditions while exhibiting efficient bactericidal function. Furthermore, the room-temperature preparation method is conducive to industrial-scale production, highlighting a better prospect for practical applications.
研究领域:
环境科学
·
材料科学
·
生物学
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产品关联
DOI
高影响因子
Small
·
2024
·
IF 13
Zhiying Gao,Jingming Yao,Jitong Yan,Jun Sun,Congcong Du,Qiushi Dai,Yong Su,Jun Zhao,Jingzhao Chen,Xiaomei Li,Hui Li,Pan Zhang,Jun Ma,Hailong Qiu,Liqiang Zhang,Yongfu Tang,Jianyu Huang
Rechargeable aprotic lithium (Li)-oxygen battery (LOB) is a potential next-generation energy storage technology because of its high theoretical specific energy. However, the role of redox mediator on the oxide electrochemistry remains unclear. This is partly due to the intrinsic complexity of the battery chemistry and the lack of in-depth studies of oxygen electrodes at the atomic level by reliable techniques. Herein, cryo-transmission electron microscopy (cryo-TEM) is used to study how the redox mediator LiI affects the oxygen electrochemistry in LOBs. It is revealed that with or without LiI in the electrolyte, the discharge products are plate-like LiOH or toroidal Li 2 O 2 , respectively. The I 2 assists the decomposition of LiOH via the formation of LiIO 3 in the charge process. In addition, a LiI protective layer is formed on the Li anode surface by the shuttle of I 3 − , which inhibits the parasitic Li/electrolyte reaction and improves the cycle performance of the LOBs. The LOBs returned to 2e − oxygen reduction reaction (ORR) to produce Li 2 O 2 after the LiI in the electrolyte is consumed. This work provides new insight on the role of redox mediator on the complex electrochemistry in LOBs which may aid the design LOBs for practical applications.
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
危险品化学品经营许可证（带存储）