ACS Catalysis
·
2024
·
IF 11.3
Hang Yu,Shanjun Mao,Bing Lu,Hao Wang,Xie Zhang,Menghui Qi,Ruiliang Gao,Yong Wang
Multicomponent reactions such as ammoxidation are highly desirable for chemical synthesis. The complicated reaction network and catalytic active sites involved, however, make it rather challenging for extensive structure–performance relationship investigations and subsequent rational design of an efficient catalyst. In this work, efficient VOx/TiO2 catalysts with concise components and exquisite structure design demonstrated 95% selectivity at 98% conversion under 2070 h–1 for 3-picoline ammoxidation. After clarifying that the oxidative dehydrogenation process is rate-limiting, we assumed that the abundance of reactive surface lattice oxygen at the interface of vanadium–titanium is the key to high productivity and suppression of oxidation side reactions since low reaction temperature is beneficial for enlarging the difference in rates of different energy barriers. In addition, rather than applying the traditional neutralization method with alkaline components, in situ formed V2O5 crystallite was subtly to cover the strong acid sites on VOx/TiO2 catalysts in that the strong adsorption of pyridine nitrogen in 3-cyanopyridine on strong acid sites can lead to severe hydrolysis side reactions.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Wei Wang,Sai Chen,Jiachen Sun,Ziyi Li,Xianhui Wang,Yiyi Xu,Zelin Wu,Donglong Fu,Chunlei Pei,Zhi-Jian Zhao,Jinlong Gong
Rational design of metal oxide-type redox catalysts for selective propylene production is of paramount importance, yet remains challenging. This paper describes the structural and electronic effect of an alkaline earth metal promoter on lattice oxygen reactivity for chemical looping oxidative dehydrogenation (CL-ODH) of propane through the configuration of core–shell-type redox catalysts, which consist of a redox-active FeVO4 core and a selective mixed alkaline earth metal oxide shell. A systematic study demonstrates that Mg is the optimal promoter among all alkali and alkaline earth metals investigated, and the formed Mg2V2O7 outer shell provides a catalytic surface for C–H activation while blocking the nonselective sites for FeVO4, typically as an oxygen carrier. The core–shell redox catalyst with a higher coverage of the Mg2V2O7 layer achieves an enhanced propylene selectivity of 80.8% at an operation temperature of 550 °C. The design strategy highlights the exploration of alkaline earth metals in redox catalysts for chemical looping processes.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2021
·
IF 13.084
Yanliang Zhou,Yicong Chai,Xiaoyu Li,Zihao Wu,Jian Lin,Yujia Han,Lin Li,Haifeng Qi,Yiming Gu,Leilei Kang,Xiaodong Wang
Selective oxidative dehydrogenation (ODH) of light alkanes to alkenes over metal oxides usually obeys a redox catalysis cycle, where the release and recovery of lattice oxygen play a key role in catalytic performance. Therefore, it remains a challenge to prepare metal oxides with limited reducibility, such as TiO2, as a dominant active component rather than as a support or modifier in this process. Here, we find a significant increase of ethane ODH performance over a layered TiO2 (M-TiO2) catalyst, which is in situ evolved from a Ti3C2Tx MXene material during the reaction. The reactivity of this M-TiO2 is 4 times higher than that of P25 TiO2, with an excellent ethylene productivity of 15.4 gC2H4 gcat–1 h–1 that outperforms the previously reported catalysts. Experimental characterizations and theoretical calculations reveal the importance of Ti and oxygen vacancy defects over M-TiO2 on the conversion of C2H6. The Ti vacancy sites can stabilize the defective structure and increase the reducibility of lattice oxygen to reduce the activation energy barrier of ethane, while the oxygen vacancy sites facilitate the activation of O2 to recover lattice oxygen.
研究领域:
催化化学
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材料科学
·
理论计算
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2020
·Vol. 8
·期 26
·13150-13159
·
IF 11.301
Huan Liu,Xiaoning Li,Cailing Peng,Liuyang Zhu,Yuanxi Zhang,Huiru Cheng,Jiameng Cui,Qingmei Wu,Yingying Zhang,Zezhi Chen,Wei Zou,Wen Gu,Haoliang Huang,Jianlin Wang,Bangjiao Ye,Zhengping Fu,Yalin Lu
The catalytic activity for the oxygen evolution reaction (OER) in electrocatalytic water splitting strongly depends on the adsorption energy of intermediates. For the generally proposed adsorbate evolution route, the universal scaling relation between the adsorption energies of *OOH and *OH leads to an OER efficiency limitation based on the “volcano curve”. A possible solution to bypass the scaling relation is to avoid the formation of the *OOH intermediate in the OER with the participation of lattice oxygen from catalysts. In this work, the lattice oxygen in (Bi0.5Co0.5)2O3 is activated through adjusting the Fermi energy level and the strong overlap between Co 3d and O 2p, by means of increasing the oxygen vacancy concentration. Compared to oxygen-vacancy-poor (Bi0.5Co0.5)2O3, the oxygen-vacancy-rich (Bi0.5Co0.5)2O3 exhibits a significantly lower Tafel slope (43 mV dec−1), 15 times higher mass activity, 18 times higher turnover frequency, and excellent long-term stability in alkaline media, superior to those of the benchmark OER electrocatalyst IrO2. This work provides a feasible strategy to activate lattice oxygen with fast OER kinetics and puts forward the development of efficient and stable catalysts towards water oxidation.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2017
·
IF 10.614
Sai Chen,Liang Zeng,Hao Tian,Xinyu Li,Jinlong Gong
Partially oxidizing methane into syngas via a two-step chemical looping scheme is a promising option for methane transformation. Providing the optimum lattice oxygen to selectively produce syngas represents the major challenge for the development of oxygen carrier materials in chemical looping processes. This paper describes the design of WO3-based oxygen carriers as the primary source of lattice oxygen with high melting points and attractive syngas selectivity. To further enhance the lattice oxygen availability and methane conversion capacity, NiO nanoclusters are introduced, considering the doping effect on chemical bonding disruption in both bulk and surface regions. For Ni0.5WOx/Al2O3, the nickel cations incorporated into the bulk of WO3 can strongly weaken the tungsten–oxygen bond strength and increase the availability of lattice oxygen. The surface-grafted nickel species can effectively activate methane molecules and catalyze the partial oxidation reaction. Total methane conversion and syngas yield can be substantially increased by about 2.7-fold in comparison with unmodified WO3/Al2O3. This work demonstrates that the bulk and surface modifications are feasible to tailor the active lattice oxygen of oxygen-carrying materials in chemical looping processes.
研究领域:
催化化学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Chemistry-An Asian Journal
·
2022
·Vol. 18
·期 1
·e202200947
·
IF 4.839
Zheng Zeng,Ma Juan Guan,Hongyu Chen,Xiang Xu,Ma Jianwu Zou,Ma Chongjie Zhang,Yankun Du,Liqing Li
Graphical As shown in the following figure, for PtFe 3 −C, toluene was directly adsorbed on the surface oxygen position and finally converted into H 2 O and CO 2 . For PtFe 3 −CeO 2 , two reaction channels containing both lattice oxygen (blue ball) from CeO 2 and surface oxygen (pink ball) and result in a better toluene catalytic performance than PtFe 3 −C. Elimination of VOCs by catalytic oxidation is an important technology. Here, a general synergistic capture-bonding superassembly strategy was proposed to obtain the nanoscale dispersed 5.8% PtFe 3 −CeO 2 catalyst, which showed a high toluene oxidation activity (T 100 =226 °C), excellent catalytic stability (125 h, >99.5%) and a good water resistance ability (70 h, >99.5%). Through the detailed XPS analysis, oxygen cycle experiment, hydrogen reduction experiment, and in-situ DRIFT experiment, we could deduce that PtFe 3 −CeO 2 had two reaction pathways. The surface adsorbed oxygen resulting from PtFe 3 nanoparticles played a dominant role, due to the fast cycling between the surface adsorbed oxygen and oxygen vacancy. In contrast, the lattice oxygen resulting from CeO 2 nanorods played an important role due to the relationship between the toluene oxidation activity and the metal-oxygen bonding energy. Furthermore, DFT simulation verified Pt sites were the dominant reaction active sites during this reaction.
研究领域:
环境科学
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL
·
2022
·
IF 8.035
Chengrui Wang,Yanhong Fang,Zhenghao Wang,Mujun Long,Dengfu Chen,Huamei Duan,Yandong Li,Guoquan Zhang
Partially oxidizing methane into syngas via a two-step chemical looping scheme was a promising option for methane transformation. Ce 2 (SO 4 ) 3 was selected to explore the performance and mechanism of methane chemical looping partial oxidation (CLPOM) to syngas. Thermodynamic and kinetic analysis forecast the Ce 2 (SO 4 ) 3 as a promising candidate for CLPOM. Compared with literature, Ce 2 (SO 4 ) 3 not only had an outstanding syngas selectivity, but also an appropriate CH 4 conversion and molar ratio, and CH 4 conversion could reach 90.5 % of thermodynamic result. As revealed via characterization, Ce 2 (SO 4 ) 3 (1 0 2) surface had the highest peak intensity and the migration of lattice oxygen played an important role in CLPOM. Some of them were tend to agglomeration and these small particles were less than 5 μm. Density functional theory calculations demonstrated that CH 4 series dehydrogenation products tended to adsorb at O site and CH 3 → CH 2 + H was the rate-determining step. The reaction of surface lattice oxygen atoms and migration of the internal lattice oxygen atoms could inhibit carbon deposition, promote CH 4 conversion and syngas generation in experiment. Compared with NiO, Ce 2 (SO 4 ) 3 had a lower energy barrier of lattice oxygen migration, which could increase the reaction rate.
研究领域:
化学工程
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 3
·1122
·
IF 4.6
Juan He,Xiaomin Xu,Hainan Sun,Tengfei Miao,Meisheng Li,Shouyong Zhou,Wei Zhou
The harmful effects on the human body from p-phenylenediamine (PPD) in hair dyes can cause allergies and even cancer. Therefore, it is particularly important to accurately control and detect the content of PPD in our daily products and environment. Here, a small amount of non-metallic elemental P doped in perovskite oxide of SrCoO3−δ(SC) forms a good catalytic material, SrCo0.95P0.05O3−δ(SCP), for PPD detection. The improved performance compared with that of the parent SC can be attributed to three contributing factors, including a larger amount of highly oxidative oxygen species O22−/O−, better electrical conductivity, and more active sites on the P5+-oxygen bonds of SCP. Moreover, the lattice oxygen mechanism (LOM) with highly active species of lattice O vacancies and adsorbed –OO for electrocatalytic oxidation of PPD by the SCP/GCE (glass carbon electrode) sensor is proposed in our work. More importantly, the SCP/GCE sensor exhibits good stability, a low limit of detection, and high reliability (error < 5.78%) towards PPD determination in real samples of hair dyes, suggesting the substantial research potential for practical applications.Keywords:lattice oxygen;phosphorus-doped SrCo0.95P0.05O3−δ;p-phenylenediamine (PPD);electrochemical sensors;hair dyes
研究领域:
材料科学
·
环境科学
·
分析化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Zhao Sun,Shufan Yu,Sam Toan,Rufat Abiev,Maohong Fan,Zhiqiang Sun
Steam reforming of methanol is a promising approach to achieving hydrogen storage, transportation, and in situ supply. However, this technology is restricted by its high CO selectivity and catalyst deactivation. In this study, CuCr2O4-based catalytic oxygen carriers are tailored for lattice oxygen participating in low-temperature methanol reforming. We found that the low-temperature activation of methanol originated from Cu–O–Cr structure intensification and highly activated lattice oxygen induction. Specifically, methanol can be activated at temperatures as low as 160 °C, on the one hand, attributed to the reinforcement of the Cu–O–Cr structure and, on the other hand, owing to the highly reactive lattice oxygen from the CuO4 tetrahedron in the CuCr2O4 spinel. Combined with XAS and Raman results, the formation of the Cu–O–Cr structure is demonstrated. The hydrogen production rate with an applied CuCr2O4-based catalytic oxygen carrier is 53.2% higher than the control group without Cu–O–Cr formulation. Satisfactory cyclic stability is retained after the 50th lattice oxygen induction and supplement cycle, ascribing to the Cu–O–Cr structure that strongly intensifies Cu–Cr2O3 interactions. DFT results reveal that the process of CH3OH → CH3O* is the rate-determining step. Compared to Cu(111) and Cr2O3(110), the tailored Cu(111)/Cr2O3(110) surface with a Cu–O–Cr structure exhibits the lowest potential barrier during this process, promoting low-temperature methanol reforming.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Lingxiang Huang,Yue Ma,Mufan Niu,Shenyong Ren,Qiaoxia Guo,Chunming Xu,Baojian Shen
Dry reforming reaction of greenhouse gas CH 4 and CO 2 was studied over Ni-Fe bimetallic catalyst, in which the composite support of C12A7-O 2- in MCM-41 was used. The isotope 13 CH 4 /D 2 O tracing experiment showed CO mainly comes from 13 CHx oxidation reaction and DH comes from CHx and D 2 O reaction, exhibiting lattice oxygen promotes CH X oxidation and water accelerate methane conversion. XPS and TPSR-MS studies exhibited the existence of lattice oxygen in catalysts produces a little H 2 O to facilitate a lower starting point at the reaction temperature. On-line MS investigation found that the trace water addition in the system accelerated the adsorption of CO 2 on support and promoted methane dissociation, the H 2 signal appears later than CO, indicating the oxidation reaction of CHx occurs after the dissociation of CO 2 . Besides, TG analysis tells us the H 2 O may consume Cα on the catalyst in time during the reaction process to remove carbon deposition.
研究领域:
化学工程
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2021
·
IF 6.707
Richuan Rao,Hanwen Liang,Chunming Hu,Huaze Dong,Xiongzi Dong,Yongqiang Tang,Song Fang,Qiang Ling
Ag-CeO 2 nanoassemblys are prepared with a simple melamine-induced thermal decomposition method. Ag-CeO 2 nanoassemblys have a structure composed of Ag nanoparticles and CeO 2 nanoparticles. For Ag-CeO 2 nanoassemblys, Ag introduction can partially or completely activate lattice oxygen species of CeO 2 nanoparticles and however, the ease of Ag-CeO 2 interface oxygen activation is strongly influenced by their pyrolysis temperature. Ag-CeO 2 nanoassemblys prepared at 350 °C have only partial activation of CeO 2 surface oxygen. If the calcination temperature increases to 400 °C, Ag-CeO 2 nanoassemblys are fully activated to form more reducible interfacial lattice oxygen and to promote their low-temperature reductivity. Although excessive calcination temperature (500 °C) induces full activation of Ag-CeO 2 interface lattice oxygen, Ag-CeO 2 nanoassemblys will construct a new Ag-CeO 2 interface that is relative difficult to reduce, causing a less amount of reducible interface lattice oxygen provided at higher temperature. Ag-CeO 2 nanoassemblys are investigated to reveal the relationship of Ag-CeO 2 interfacial oxygen activation and CO catalytic oxidation performance. Ag-CeO 2 nanoassemblys with more interfacial lattice oxygen provided at lower temperature are found to have higher catalytic activity than that catalyst with the partially or excessively activated interfacial oxygen.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-12
·
IF 15.7
Wu Qinyue,Fan Xinfei,Shan Bing,Qi Liang,Quan Xie,Liu Yanming
Electrocatalytic NO 3 − reduction (eNO3RR) is a sustainable method for purification of NO 3 − wastewater and NH 3 recovery. Cu-based catalysts are promising for eNO3RR, but insufficient active hydrogen (*H) supply and *NO 2 poison of active sites have hindered their performance, and the catalytic mechanism remains ambiguous. Here, we report oxide-derived copper nanosheet arrays (OD-Cu NSs) with residual lattice oxygen and lattice strains to enhance NH 3 synthesis from eNO3RR. It is efficient for NH 3 synthesis with high Faradaic efficiencies of 88.7-99.7% and maximum NH 3 yield of 6.20 mmol·h −1 ·cm −2 at neutral solution, 10-140 mM NO 3 − and 50-1500 mA·cm −2 . Experimental and theoretical results reveal that lattice oxygen regulates the electronic structure of OD-Cu NSs and promotes *NO 2 conversion, while lattice strain enhances *H generation from water dissociation, resulting in the good performance for NH 3 synthesis. The applicability of OD-Cu NSs is proved by the high recovery of ammonia compound from eNO3RR.
研究领域:
电催化
·
材料科学
·
环境科学
✓ 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）