Journal of the American Chemical Society
·
2025
·
IF 15.6
Jun Mao,Huan Liu,Yanan Li,Meng Gao,Yunlong Zhang,Yao Song,Mo Zhang,Guilan Xu,Wu Zhou,Liang Yu,Xiaoju Cui,Dehui Deng
The oriented conversion of CH4 to CH3COOH at low temperature, even room temperature, is both scientifically significant and industrially applicable for CH4 utilization, yet it is extremely challenging due to the difficulties associated with efficient CH4 activation and controllable C–C coupling. In this study, we for the first time achieve the room-temperature conversion of CH4 to CH3COOH using molecular O2 and CO over MoS2-confined Rh–Fe sites, which delivers an unprecedented CH3COOH selectivity of 90.3% and a productivity of 26.2 μmol gcat.–1 h–1 at 25 °C. Furthermore, the productivity of CH3COOH can be enhanced to 105.6 μmol gcat.–1 h–1 at 80 °C, while maintaining a high selectivity of 95.6%. Comprehensive experimental and theoretical investigation reveal the critical role of Rh–Fe synergy in the selective formation of CH3COOH. The confined Fe sites in MoS2 enable the activation of O2 to generate highly reactive Fe═O center for CH4 dissociation to CH3 species at room temperature, which then readily couple with adsorbed CO on adjacent Rh sites to form the key CH3CO intermediate for CH3COOH production. The unique structure of Rh–Fe sites offers synergistic catalytic properties that effectively balance C–H activation and C–C coupling, successfully addressing the trade-off between activity and selectivity in the carbonylation of CH4 to CH3COOH under mild conditions.
研究领域:
化学
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催化反应
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Energy Technology
·
2019
·Vol. 7
·期 7
·1801128
·
IF 3.163
Weicheng Cui,Hongye Bai,Konggang Qu,Fagen Wang,Peng Guan,Dongbo Xu,Weiqiang Fan,Weidong Shi
Kinetics play a critical role in the photoelectrochemical (PEC) system, whereas co-catalysis is mainly responsible for reducing the reaction barrier and facilitates water splitting. Here, the unsaturated Fe sites through the metal-organic framework (MOFs) structure promote the kinetics of water oxidation over TiO 2 are successfully in situ decorated. This heterostructure further helps us to better understand the PEC behaviors of organic–inorganic hybrid systems. MIL-100(Fe), as the typical MOFs model, is facilely achieved by an FeOOH sacrificial template method, a strategy which could anchor the compact and ultrathin MIL-100(Fe) films on the surface of TiO 2 to obtain abundant unsaturated Fe sites. The photocurrent density of MIL-100(Fe)/TiO 2 reaches about 2.4 times at 1.23 V vs reversible hydrogen electrode (RHE) compared with bare TiO 2 , and the incident photon to current conversion efficiency value increases up to 47% (at 390 nm). Furthermore, the photocurrent density of MIL-100(Fe)/TiO 2 is maintained at 84% after 3 h, showing that the organic component of MIL-100(Fe) takes a nature of favorable stability. The configuration of MIL-100(Fe)/TiO 2 will bring a new insight for learning the basic function of unsaturated metal sites in the PEC system.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Environmental Science-Water Research & Technology
·
2024
·
IF 3.5
Haoxiang Yan,Jianzheng Zhen,Yuyuan Yao
Developing a facile preparation method to construct separable and recyclable Fenton-like catalysts holds great significance in the field of environmental remediation. Herein, a rapid dopamine (DA) polymerization strategy to modify melamine foam (MF) was proposed for the construction of bulk foam catalytic materials, which was further utilized for peroxymonosulfate (PMS) activation to degrade organic pollutants. Taking advantage of the chelation between dopamine's catechol group and Fe3+, as well as the oxidative environment provided by H2O2, DA could encapsulate and polymerize on the surface of MF within 2 h to obtain the MF@Fe@PDA catalyst. Detailed experimental results demonstrated that MF@Fe@PDA could efficiently activate PMS to achieve almost 100% removal of bisphenol A (BPA) in 20 min, and the corresponding turnover frequency (TOF) value was one order of magnitude higher than that of the homogeneous (Fe2+, Fe3+) and nanoparticle (Fe0) catalysts. The high activity of the MF@Fe@PDA/PMS system stemmed from the Fe sites and carbonyl group (CO), which could induce the activation of PMS for the rapid generation of singlet oxygen (1O2), sulfate radical (SO4˙−) and hydroxyl radicals (˙OH). Meanwhile, the coexisting bicarbonate ions (HCO3−) in the MF@Fe@PDA/PMS system could enhance the generation of 1O2, thereby accelerating the degradation of BPA. Moreover, a flow-through system assisted by the bulk MF@Fe@PDA catalyst was constructed for organic pollutant degradation. Overall, these findings may open up new possibilities for developing highly efficient catalysts for wastewater remediation.
研究领域:
环境科学
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催化材料
✓ 已验证
产品关联
DOI
高影响因子
ACS Nano
·
2018
·
IF 13.709
Sufeng An,Guanghui Zhang,Tingwen Wang,Wenna Zhang,Keyan Li,Chunshan Song,Jeffrey T. Miller,Shu Miao,Junhu Wang,Xinwen Guo
Ultra-small metal clusters have attracted great attention owing to their superior catalytic performance and extensive application in heterogeneous catalysis. However, the synthesis of high-density metal clusters is very challenging due to their facile aggregation. Herein, one-step pyrolysis was used to synthesize ultra-small clusters and single-atom Fe sites embedded in graphitic carbon nitride with high density (iron loading up to 18.2 wt %), evidenced by high-angle annular dark field-scanning transmission electron microscopy, X-ray absorption spectroscopy, X-ray photoelectron spectroscopy, and 57Fe Mössbauer spectroscopy. The catalysts exhibit enhanced activity and stability in degrading various organic samples in advanced oxidation processes. The drastically increased metal site density and stability provide useful insights into the design and synthesis of cluster catalysts for practical application in catalytic oxidation reactions.
研究领域:
材料科学
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环境化学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Chen Qiao,Zahid Usman,Tai Cao,Souleymen Rafai,Zhitao Wang,Youqi Zhu,Chuanbao Cao,Jiatao Zhang
High-valence Ni and Fe metal sites have demonstrated a crucial role in enhancing the catalytic performances of NiFe-LDH electrocatalysts in oxygen evolution reaction (OER). Although considerable OER catalytic performances achieved under high overpotential, the catalytic talent of NiFe-LDH electrocatalysts at low overpotential is rarely realized due to the absence of high-valence Ni and Fe sites. We herein report a surface engineering route to fabricate sulfated NiFe-LDH nanosheets via ion exchange strategy in sulfate-rich media. XPS results reveal a modified surface electronic structure with high-valence Ni and Fe after ion exchange reaction. Computational PDOS results suggest that computed d-band centers (ε d ) of Fe and Ni for sulfated NiFe-LDH show a significant downward shift resulting an increased valence of metal cation with orbital volume shrinkage. The high-valence Fe can facilitate a optimized multi-electron process of Ni center from [Ni II -OH] − /[Ni III -OH] − to Ni IV -OOH rather than Ni II /Ni III to Ni IV at low overpotential. The high-valence Ni can serve as the highly active center for O-O coupling during OER process. Combined with the synergetic action of high-valence Fe and Ni, the sulfated NiFe-LDH nanosheets exhibit much larger reaction kinetics and outstanding electrocatalytic activity on glassy carbon electrode (η 10 = 219 mV, η 50 = 288 mV) with a remarkable long-term stability.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
DOI
高影响因子
Nature Catalysis
·
2022
·Vol. 5
·期 6
·503-512
·
IF 40.706
Xiao Fei,Wang Qi,Xu Gui-Liang,Qin Xueping,Hwang Inhui,Sun Cheng-Jun,Liu Min,Hua Wei,Wu Hsi-wen,Zhu Shangqian,Li Jin-Cheng,Wang Jian-Gan,Zhu Yuanmin,Wu Duojie,Wei Zidong,Gu Meng,Amine Khalil,Shao Minhua
Proton exchange membrane fuel cells convert hydrogen and oxygen into electricity without emissions. The high cost and low durability of Pt-based electrocatalysts for the oxygen reduction reaction hinder their wide application, and the development of non-precious metal electrocatalysts is limited by their low performance. Here we design a hybrid electrocatalyst that consists of atomically dispersed Pt and Fe single atoms and Pt–Fe alloy nanoparticles. Its Pt mass activity is 3.7 times higher than that of commercial Pt/C in a fuel cell. More importantly, the fuel cell with a low Pt loading in the cathode (0.015 mg Pt cm −2 ) shows an excellent durability, with a 97% activity retention after 100,000 cycles and no noticeable current drop at 0.6 V for over 200 hours. These results highlight the importance of the synergistic effects among active sites in hybrid electrocatalysts and provide an alternative way to design more active and durable low-Pt electrocatalysts for electrochemical devices.
研究领域:
材料科学
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电化学
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能源技术
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
·
IF 15.7
He Xun,Yao Yongchao,Zhang Min,Zhou Yilei,Zhang Limei,Ren Yuchun,Dong Kai,Tang Hong,Nan Jue,Zhou Xingli,Luo Han,Ying Binwu,Yu Qi,Luo Fengming,Tang Bo,Sun Xuping
Seawater electrolysis driven by offshore renewable energy is a promising avenue for large-scale hydrogen production but faces challenges in designing robust anodes that suppress surface chlorine reactions and corrosion at high current densities. Here we report a strategy by selectively docking PW 12 -polyoxometalate (PW 12 -POM) onto Fe sites of CoFe hydroxide anode to modulate the electronic structure of adjacent Co active centers and regulate Cl⁻/OH⁻ adsorption for efficient alkaline seawater oxidation. Our CoFe-based anode achieves low overpotentials, high catalytic selectivity, and notable durability, with continuous operation at 1 A cm⁻² for over 1300 hours and at 2 A cm⁻² more than 600 hours. Theoretical calculations and ex situ/in situ analyses reveal that PW 12 -POM coordination at Fe sites stabilizes Fe, suppresses its leaching, modulates Co acidity, promotes OH⁻ adsorption, and protects metal sites from Cl⁻ corrosion.
研究领域:
电化学
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材料科学
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能量转换
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催化
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可再生能源
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表面化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Qiyu Li,Lei Zhao,Zhaozhao Zhu,Pei Xiong,Jiayu Zuo,Jun Song Chen,Rong Li,Rui Wu
Zinc-air batteries (ZABs) have garnered significant interest due to their environmental friendliness, low cost, and high energy density. However, their practical application is significantly hindered by high overpotential and sluggish reaction kinetics. Here, we propose a hollow nitrogen-doped carbon supported atomically dispersed Fe and Mn sites (FeMn-HNC) through a facile NaCl-assisted pyrolysis strategy. The synthesized FeMn-HNC catalyst possesses a hollow porous structure, resulting in exceptional oxygen reduction reaction (ORR) catalytic activity, remarkable durable stability, and good tolerance to methanol. Furthermore, integrating this catalyst into ZABs demonstrates significant performance advantages, achieving a maximum power density of 223.1 mW cm −2 and a high specific capacity of 804.3 mAh g −1 . This study offers a promising approach for boosting the power density and specific capacity of nitrogen-doped carbon catalysts in ZABs.
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
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Wenxuan Zhou,Xiaoyong Mo,Cham Wah Cheung,Edmund C.M. Tse
At present, over 95 % of H 2 O 2 is produced via the anthraquinone process that requires large infrastructure, generates organic pollution, and poses safety issues. Electrochemical H 2 O 2 generation through oxygen reduction can serve as an alternative, reliable, and decentralized production method if affordable and high-performance electrocatalysts can be developed. Herein, a two-step process is used to prepare an Fe-based complex as a non-precious metal electrocatalyst to facilitate oxygen reduction reaction (ORR) and produce an alkaline H 2 O 2 solution. The Fe complex of benzene-1,3,5-tricarboxylate (FeBTC) is first synthesized using a hydrothermal method and then activated via a pulsed laser treatment process that is optimized via the Taguchi method. The pulse-laser-treated FeBTC (PL-FeBTC) lowers the H 2 O 2 electrosynthesis overpotential by 50 mV at −0.1 mA/cm 2 and exhibits a 25 % increase in H 2 O 2 product selectivity at 0.4 V vs. RHE. The experimental results indicate that the O 2 -to-H 2 O 2 turnover frequency and electrocatalytic yield of the Fe-based metal–organic framework are enhanced simultaneously through solid-to-solid pulsed laser conversion. Through a series of X-ray photoelectron spectroscopy, elemental analysis, Raman spectroscopy, X-ray absorption spectroscopy, and control atmospheric experiments, the origin of the improvement in catalytic performance is rationalized through the formation of an oxo-bridge across the di–Fe active site via an oxygen-doping mechanism, thus providing a systematic laser methodology for precise structure-performance tuning. Beyond H 2 O 2 generation, this study further lays the foundation for the development of cost-effective and scalable electrocatalysts that are central to other commodity manufacturing and sustainable resourcification processes.
研究领域:
材料科学
·
电化学
·
催化
·
可持续化学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）