Journal of Materials Chemistry A
·
2023
·Vol. 11
·期 26
·14043-14051
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IF 11.9
Guang Li,Zheng-Chao An,Jian Yang,Jin-Hong Zheng,Li-Fei Ji,Jun-Ming Zhang,Jin-Yu Ye,Bin-Wei Zhang,Yan-Xia Jiang,Shi-Gang Sun
The electrochemical performance of Pt-based catalysts depends on their surface structure. Nevertheless, it is still a challenge to investigate their intricate surface-active sites. Here, PtAu films were utilized as model catalysts to understand the surface fine structure and structure–activity relationship. Significantly, the in situ attenuated total reflectance-surface enhanced infrared absorption spectroscopy (ATR-SEIRAS) CO-probe method was established to reveal the surface-active sites of PtAu catalysts. By employing the second derivative spectrum (SDP) method and Gaussian fitting for the infrared spectra of the CO oxidation reaction (COR), three surface configurations, the PtisoAu, PtadjAu site and PtrichAu site, were unveiled. Additionally, the activity order and reactive species of the COR oxidation peaks were clarified by correlating COL intensities with the COR current curves. More importantly, this in situ ATR-SEIRAS CO-probe strategy can be extended from PtAu model films to PtAu nanoparticles.
研究领域:
催化化学
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材料科学
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红外光谱学
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产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-9
·
IF 16.6
Zhang Li,Yang Xiaoju,Yuan Qing,Wei Zhiming,Ding Jie,Chu Tianshu,Rong Chao,Zhang Qiao,Ye Zhenkun,Xuan Fu-Zhen,Zhai Yueming,Zhang Bowei,Yang Xuan
Understanding the structure-stability relationship of catalysts is imperative for the development of high-performance electrocatalytic devices. Herein, we utilize operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) to quantitatively monitor the evolution of Cu single-atom catalysts (SACs) during the electrochemical reduction of CO 2 (CO 2 RR). Cu SACs are converted into 2-nm Cu nanoparticles through a reconstruction process during CO 2 RR. The evolution rate of Cu SACs is highly dependent on the substrates of the catalysts due to the coordination difference. Density functional theory calculations demonstrate that the stability of Cu SACs is highly dependent on their formation energy, which can be manipulated by controlling the affinity between Cu sites and substrates. This work highlights the use of operando ATR-SEIRAS to achieve mechanistic understanding of structure-stability relationship for long-term applications.
研究领域:
催化
·
电化学
·
表面科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Shaojian Jiang,Yuhang Liu,Ruidong Yang,Kai Deng,Ziqiang Wang,You Xu,Liang Wang,Hongjie Yu,Hongjing Wang
Propylene glycol (PG) demands sustainable electrochemical synthesis to overcome the environmental and economic drawbacks of thermochemical processes. The activation of reactive oxygen species (ROS) represents a critical determinant in optimizing the electrocatalytic oxidation of propylene (Pr) to PG. Here, we propose a lattice oxygen involving mechanism (LOM) to enhance *OH generation and Pr activation, achieving direct conversion of Pr to PG using Mn 3 O 4 nanoparticle-loaded Pd metallene (Mn 3 O 4 /Pdene). Mn 3 O 4 /Pdene achieves 86.5 % PG selectivity and 55.4 % Faradaic efficiency at 1.15 V via LOM pathway with stable performance over 80 h. In situ ATR-SEIRAS, 18 O isotope labeling experiments, and in situ differential electrochemical mass spectrometry (DEMS) validate the LOM pathway: Lattice-O activates Pr through C-O-C bond formation, while *OH from lattice-O attacks tertiary carbons to generate *PrOH, with water-derived *OH replenishing lattice-O for PG synthesis. DFT reveals that the LOM pathway facilitates H 2 O dissociation and C C bonds polarization, lowering the rate-determining step energy barrier. This work highlights the role of lattice oxygen in the electrocatalytic propylene oxidation and unveils a novel LOM pathway of propylene oxidation.
研究领域:
电化学
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催化
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材料科学
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化学工程
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物理化学
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产品关联
DOI
高影响因子
FUEL
·
2023
·
IF 7.4
Mei Luo,Xiangmin Fu,Shuo Geng,Ziwei Li,Min Li
CO 2 electrocatalysis reduction (CO 2 RR) is considered to be one of the most efficient methods to achieve carbon neutralization and realize renewable energy conversion. Unfortunately, at present, CO 2 electrocatalysts confront the challenges of high overpotential, low selectivity, and poor stability. Ag based electrocatalysts are considered to be the most promising catalysts for CO production via CO 2 RR on a large scale, due to their relatively higher catalytic performance and more abundant reserves compared with other noble metals. Whereas, they still suffer from high cost. In this paper, we design bimetallic CuAg/CeO 2 -6 catalysts by the simple impregnation method for CO 2 RR, exhibiting the highest FE CO of 84% at –1.1 V vs. RHE compared with other bimetallic catalysts with different Cu/Ag ratio and monometal catalysts. XPS results demonstrate the electron delocalization effect not only between Cu and Ag bimetals but also among CeO 2 support. This effect results in the electronic structure change and the formation of the highest concentration of oxygen vacancies, promoting the CO 2 adsorption and activation as well as facilitating the formation of COOH* intermediates as evidenced by the in situ ATR-SEIRAS measurements. Additionally, the highest active surface for CO 2 RR and the smallest charge resistance of CuAg/CeO 2 -6 also contributes to its good CO 2 RR performance. This work sheds light on the design of other efficient CO 2 RR catalysts through electronic structure tuning by bimetallic strategy.
研究领域:
电化学
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催化
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材料科学
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可再生能源
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产品关联
DOI
高影响因子
Small
·
2025
·
IF 12.1
Zipei Cui,Yipeng Nie,Longquan Deng,Zhuo Li,Shuo Chen,Wenchao Sheng
Promoting C─C bond cleavage of ethanol to achieve a complete 12-electron pathway (C1 pathway) for ethanol oxidation reaction (EOR) is crucial for the development of highly efficient direct ethanol fuel cells. In this study, a highly porous ultrathin PdSn nanomesh (NM) with high proportion of low-coordinated edge and step sites is developed for alkaline EOR. The PdSn NM/C catalyst exhibited superior specific activity of 21.9 ± 0.9 mA cm −2 Pd with a significantly enhanced Faradaic efficiency of C1 pathway to CO 2 . In situ attenuated total reflection surface enhanced infrared absorption spectroscopy measurements demonstrated the significant enhancement of C1 selectivity on PdSn NM/C. Theoretical calculations further revealed the pivotal role of low-coordinated edge and step sites in effectively lowering the activation energy barrier for C─C bond cleavage of CH 3 CO*. This work provides a strategy for the rational design of highly efficient EOR electrocatalysts through low-coordinated site engineering.
研究领域:
电催化
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材料科学
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能量转换
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纳米材料
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燃料电池
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产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2025
·
IF 9.5
Yu Liu,Rong Peng,Ying Xu,Xiaoqiong Liu,Yi Song,Wenwei Liu,Wu Tianli,Junwei Zhang,Tao Li
Glycerol, as a renewable fuel with high energy density, has broad application prospects in green energy conversion.However, its electrocatalytic oxidation is limited by the activity and selectivity of catalysts, which severely restricts the efficient release of energy. In this work, we report a facile co-reduction synthesis of bimetallic Au-Ti nanoparticles featuring abundant Au-TiO x interfaces, which nearly doubled the mass activity for glycerol electrooxidation from 1.420 A mg Au -¹ to 2.717 A mg Au -¹, and presented an impressively high mass activity retention after the stability test. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) analysis confirms that Au-Ti alloy shows a deeper oxidation behaviour. Density functional theory (DFT) calculations further reveal that the formation of Au-TiO x interfaces gives rise to bifunctional synergistic sites, which facilitate the cooperative adsorption of glycerol and hydroxyl species, thereby overcoming the limitations of single-type active sites on Au/C. Meanwhile, CO adsorption further enhances the binding of hydroxyl groups, synergistically promoting deep oxidation of glycerol.
研究领域:
电催化
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纳米材料
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可再生能源
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表面科学
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物理化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-10
·
IF 16.6
Ding Jie,Wei Zhiming,Li Fuhua,Zhang Jincheng,Zhang Qiao,Zhou Jing,Wang Weijue,Liu Yuhang,Zhang Zhen,Su Xiaozhi,Yang Runze,Liu Wei,Su Chenliang,Yang Hong Bin,Huang Yanqiang,Zhai Yueming,Liu Bin
In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co 2+ can enhance the electron backdonation via the d xz / d yz −2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.
研究领域:
电化学
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催化
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材料科学
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理论化学
✓ 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）