ACS Sustainable Chemistry & Engineering
·
2026
·Vol. 14
·期 35
·16045-16056
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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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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
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材料科学
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环境科学
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ACTA PHYSICO-CHIMICA SINICA
·
2014
·Vol. 30
·期 1
·150-156
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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
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电化学
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能源存储与转换
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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
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纳米技术
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癌症治疗
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材料科学
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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
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材料科学
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生物学
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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
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电化学
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能源存储
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CERAMICS INTERNATIONAL
·
2024
·
IF 5.1
Xinyu Ping,Bin Meng,Xiaohua Yu,Qingqing Yang,Zhiyuan Ma,Xiaoyu Pan
A medium-entropy fluorite-structured ceramic of (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ was prepared using a solid state reaction method combined with conventional sintering at 1600 ° C for 10 h. This ceramic has uniform elemental distribution without impurity and segregation. The annealing experiment results show a reversible transformation between single phase and double phases in (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ in 800–1600 °C. The reversible phase transformation does not display any obvious influence on the thermal expansion of this sample. The thermal expansion coefficient of (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ is 12.4 × 10 −6 K −1 in 100–1500 °C, higher than that of 8 wt% yttria-stabilized zirconia (8 YSZ). Furthermore, (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ possesses a lower thermal conductivity (1.51 W m −1 K −1 at 900 ° C) and higher oxygen barrier property compared with 8 YSZ at high temperature. The Vickers' hardness, Young's modulus and fracture toughness of (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ are 10.0 GPa, 193.9 GPa and 1.93 MPa m 1/2 , respectively. These results demonstrate that (Y 0·25 Zr 0.25 Hf 0.25 Ce 0.25 )O 2−δ can be used as a promising candidate ceramic of thermal barrier coatings.
研究领域:
材料科学
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热物理性质
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陶瓷材料
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Materials Today Communications
·
2024
·
IF 3.7
Zhiqin Wen,Zhenyu Wu,Bo Ma,Jiedong Qin,Li Tang,Taoyi Lu,Yuhong Zhao
A novel 6-cationic single-phase high-entropy fluorite oxides (HEFOs) (Ce 0.16 Zr 0.16 La 0.16 Sm 0.16 Nd 0.16 Y 0.16 )O 2- δ (CZLSNYO) have been prepared by using solid-state reactions, and the structure and mechanical properties of the HEFOs were studied in depth. CZLSNYO exhibits a single-phase cubic fluorite structure with a smooth and crack-free surface and distinct grain boundaries after sintering at 1400 °C, 1500 °C and 1600 °C for 12 hours. The concentration of Ce 3+ in Ce ions is calculated to be 22.23 % ± 1.11 %, and the value of δ is 0.3519 ± 0.0176, yielding a nominal composition of (Ce 0.16 Zr 0.16 La 0.16 Sm 0.16 Nd 0.16 Y 0.16 )O 1.6481 ± 0.0176 . With the increase of sintering temperature, the average grain size of CZLSNYO initially enlarges and then reduces, and its Vickers hardness exhibits a comparable trend. By comparing with the 5-cations (Ce 0.2 Zr 0.2 La 0.2 Sm 0.2 Nd 0.2 )O 2- δ HEFOs, 6-cationic single-phase CZLSNYO sintered at 1500 °C possess large hardness (16.32 GPa) and fracture toughness (8.07 MPa m 1/2 ), since the addition of Y element increases the configuration entropy of the system, and Y has a greater hardness, resulting in a cocktail effect.
研究领域:
材料科学
·
化学
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JOURNAL OF POROUS MATERIALS
·
2024
·
IF 2.5
Tang Yingying,Xia Yongfeng,Yao Dongxu,Zhu Ming,Zhao Jun,Zeng Yu-Ping
Thermal insulation materials must exhibit superior mechanical properties alongside exceptional thermal insulation conductivity. However, traditional porous ceramics often struggle to meet these dual requirements simultaneously. In high-entropy materials, the phonon scattering induced by lattice distortion effects can significantly reduce the thermal conductivity of ceramics, thus opening new avenues for the design of novel thermal insulation materials. Inspired by the high-entropy effect, this study employed solid-state reaction methods to synthesize (Ce 0.2 Zr 0.2 Ti 0.2 Sn 0.2 Ca 0.2 )O 2−δ (CZTSC) high-entropy ceramics at various temperatures, investigating their phase constituents, microstructural characteristics, and mechanical properties, while exploring the optimal sintering temperature. Additionally, a pore-forming agent method was utilized to fabricate monophasic CZTSC porous ceramics with different porosities at 1400 °C. Specifically, when the pore-forming agent content was 20 wt%, the sample exhibited an apparent porosity of 42.82%, with a low thermal conductivity of 0.57 W·m − 1 ·K − 1 , a low thermal diffusivity of 0.406 mm 2 ·s − 1 , and a relatively high compressive strength of 32.49 MPa. The current investigation underscores the promising prospects of porous CZTSC ceramics in the field of thermal insulation.
研究领域:
材料科学
·
热能工程
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Haonan Zhang,Changhe Lu,Shuai Wang,Qinhua Zhang,Qiang Zhou,Shuxu Zhu,Chong Qi,Mingbo Wu,Wenting Wu
The utilization of O 2 for propylene epoxidation is a highly desirable reaction due to its 100 % atom economy. However, achieving this reaction under mild conditions presents a significant challenge. In this paper, we present a tandem reaction system that combines 4,4′-dibromobenzophenone (BP) modified carbon nitride (g-C 3 N 4 ) with titanium silicalite zeolite (TS-1) to enable the selective photooxidation of propylene into propylene oxide at room temperature, using O 2 as the oxygen source. The achieved production rate of propylene oxide was an impressive 1195 μmol/g cat. /h, with a selectivity exceeding 99 %. Furthermore, the catalyst exhibited no significant deactivation after 5 cycles. Spectra and in-situ capture experiments revealed that the reaction involved a two-step system, with photocatalytic production of H 2 O 2 and propylene epoxidation facilitated by H 2 O 2 ·H 2 O 2 was generated through O 2− and 1 O 2 pathways, with an in-situ utilization efficiency of H 2 O 2 reaching 82 %. This work presents a novel approach for the direct epoxidation of propylene using O 2 .
研究领域:
化学工程
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环境科学
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材料科学
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高影响因子
LANGMUIR
·
2025
·
IF 3.9
Dexi Yu,Yuhong Lin,Wenhui Zhou,Xiaoyi Wang,Zhenzhen Yu,Yidong Hou,Masakazu Anpo,Jimmy C. Yu,Jinshui Zhang,Xinchen Wang
Photocatalytic oxidation of benzene to phenol using molecular O2 is one of the most promising sustainable approaches for the green synthesis of phenol. Introducing oxygen vacancies (OVs) on semiconductor surfaces by defect engineering is a promising strategy to enhance the efficiency of benzene oxidation to produce phenol due to the unique functions of OVs in facilitating the charge separation and activation of molecular O2. Herein, a vacuum-sealed annealing strategy has been well developed to generate abundant surface OVs on semiconductors, such as WO3. The well-sealed quartz vial creates a well-controlled low-pressure condition for the formation of OVs without the need for external energy for maintaining the vacuum state. Moreover, the gaseous species generated during the thermal annealing process help mitigate stress-induced defects, particularly bulk defects. The vacuum-sealed annealed WO3 with sufficient OVs and reduced bulk defects shows a better photocatalytic performance in the one-step oxidation of benzene to phenol with O2, compared to the WO3 synthesized through thermal annealing in Ar and H2 atmospheres. The present vacuum-sealed annealing strategy is found to be further applicable to engineer a wide range of semiconducting photocatalysts with abundant OVs to optimize their properties for efficient photocatalysis and other OV-promoted systems.
研究领域:
材料科学
·
环境科学
·
化学工程
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PubMed
高影响因子
FUEL
·
2024
·
IF 6.7
Wenheng Hu,Huan Chen,Junjie Wang,Zhe Zhang,Zhengliang Zhang,Dawei Song,Yaqin Shi,Donghui Long,Yayun Zhang
Transforming alkanes into value-added light aromatics represents an promising strategy for maximizing the utility of fossil feedstocks. However, achieving highly selective aromatization reactions remains a formidable challenge. This study advocates for an alkane-O 2 coupling reaction strategy, which involves introducing a low-concentration O 2 atmosphere into the reaction system to facilitate the upgrading of alkanes to value-added aromatics over HZSM-5 zeolite catalyst. The investigation revealed that the abundant acidic sites on the zeolite facilitated alkane activation and subsequent C–C and C–H bond cleavage. Incorporating O 2 into the reaction generated oxygenated intermediates, significantly enhancing both the yield and selectivity of light aromatics compared to an inert atmosphere. Furthermore, the interaction of O 2 with coke bolstered the catalyst’s resistance to coking. Moreover, based on the in-situ FTIR results, a plausible alkane-O 2 coupling mechanism is proposed. These findings present a novel, effective, and environmentally benign approach for the highly selective aromatization of alkanes.
研究领域:
化学工程
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催化
·
石油化学
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高影响因子
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