Catalysts
·
2022
·Vol. 12
·期 9
·955
·
IF 4.501
Beilei Cui,Hua Wang,Qingfeng Ge,Xinli Zhu
A series of rutile TiO2-supported Ni catalysts with varying Ni sizes were prepared and reduced at 650 °C to explore the effect of Ni size on the strong metal–support interactions (SMSI) and its consequences on the hydrodeoxygenation (HDO) of m-cresol at 350 °C and atmospheric pressure. When the Ni size increases from 4 to 29.1 nm, the SMSI becomes stronger, e.g., the thickness of the TiOxoverlayer and the coverage extent of TiOxon the Ni particle surface increase. Direct deoxygenation to toluene is the dominant pathway on Ni/TiO2catalysts with varying Ni loadings, with almost no CH4being formed. These results indicate that the TiOxoverlayer significantly alters the property of Ni. That is, the C-C hydrogenolysis activity on bare Ni is completely inhibited due to SMSI, while the deoxygenation activity is improved at the Ni-TiOxinterfacial perimeter sites. Meanwhile, the turnover frequency of HDO on small Ni particles of 4 nm is > 2 times higher than that on large Ni particles of 29.1 nm, indicating that the small Ni particle with moderate SMSI appears to be optimal for the direct deoxygenation of m-cresol to toluene. The results suggest HDO activity may be enhanced by tuning the metal particle size and SMSI degree.Keywords:Ni/TiO2;rutile;strong metal-support interactions;m-cresol;hydrodeoxygenation
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF RARE EARTHS
·
2019
·
IF 2.846
Wenfeng Han,Zhi Li,Huazhang Liu
La 2 Ce 2 O 7 nanoparticles were prepared by citric acid complexation method followed by calcination at varied temperatures. Then, supported with 4 wt% Ru, they were evaluated as the catalysts for ammonia synthesis under conditions similar with industry. With La 2 Ce 2 O 7 being calcinated at 700 or 800 °C, the experimental results indicate that the Ru/La 2 Ce 2 O 7 catalyst exhibits much higher ammonia concentration or ammonia synthesis rate than that of Ru/CeO 2 and Ru/La 2 O 3 . In addition, Ru/La 2 Ce 2 O 7 possesses high stability under over-heating test. In the absence of any promotor, ammonia concentration of Ru/La 2 Ce 2 O 7 catalyst approaches 14% at 450 °C, GHSV of 10000 h −1 and pressure of 10 MPa. The rate-determining step of ammonia synthesis, dissociation of N 2 is significantly facilitated by the strong metal–support interaction (SMSI) between Ru and La 2 Ce 2 O 7 . Due to the interaction, La 2 Ce 2 O 7 tends to donate electrons to Ru, resulting in the high electron density over the surface of Ru active sites which is favorable for the dissociation of N 2 . Consequently, high activity is achieved.
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
ADVANCED MATERIALS
·
2024
·
IF 27.4
Yu Zhang,Qin Zhao,Bukhvalov Danil,Weiping Xiao,Xiaofei Yang
The Pt-based alloys can moderate the binding energies of oxygenated species on the catalytic surface, endowing the superior catalytic performance towards oxygen reduction reaction (ORR). Nevertheless, it is still challenging to explore general methods to synthesize structurally ordered intermetallics with uniform distributions. Herein, the strong metal-support interaction is employed to facilitate the interdiffusion of Pt/M atoms by establishing a tunnel of oxygen vacancy on ultrathin Ti 3 C 2 T x (MXene) sheets, synthesizing the ordered PtFe, PtCo, PtZn, PdFe, PdZn intermetallics loaded onto Ti 3 C 2 T x . Furthermore, the in-situ generation of Ti–O from Ti 3 C 2 T x could be bonded with Pt and forming Pt–O–Ti, resulting in charge redistribution through Pt–O–Ti structure. Theoretical calculations demonstrate that the valuable charge redistribution can be observed at the interface and extended even to at the distance of two nanometers from the interface, which can modulate the Pt–Pt distance, optimize Pt–O binding energy and enhance intrinsic activity towards ORR. The strong coupling interaction between PtFe and Ti 3 C 2 T x containing the titanium oxide layer endows the high stability of the composites. This work not only presents a general synthesis strategy for intermetallics but also provides a new insight that metal-support interaction is essential for the structural evolution of intermetallics on materials with oxygen vacancies.
研究领域:
材料科学
·
电化学
·
催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Qiang Fu,Lei Lin,Tao Wu,Qinghua Zhang,Xianjie Wang,Lingling Xu,Jun Zhong,Lin Gu,Zhihua Zhang,Ping Xu,Bo Song
Precious metals (Pt, Ir, Ru, and so on) and related compounds usually demonstrate superb catalytic activity for electrochemical hydrogen production. However, scarcity and stability are still challenges for hydrogen evolution reaction, even for single-atomic-site electrocatalysts. Herein, a fluorine (F) doping strategy is proposed to enhance the strong metal–support interaction between the F-doped Ni3N support and the loaded ruthenium (Ru) species. Via synergistically modulating both the Ru loading amount and F doping concentration, outstanding HER activity was achieved in Ru@F–Ni3N with an overpotential (η) of 115 mV at 100 mA cm–2, superior to the benchmark Pt/C (η = 201 mV). Density functional theory simulation in combination with X-ray photoelectron spectra and X-ray absorption spectroscopy characterizations convincingly demonstrate that, with the strongest electronegativity, F doping could effectively stabilize Ru atoms doped in the F–Ni3N substrate and simultaneously reduce the H bonding strength, which accelerated the desorption of H2. These findings provide a facile strategy to modulate both catalytic activities and stabilities of heteroatom-loaded catalytic materials.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Wenqian Shen,Qiang Fu,Chi Shing Tsang,Lok Wing Wong,Xiaodong Zheng,Jiong Zhao,Thuc Hue Ly
Strong metal-support interaction (SMSI) plays a critical role in enhancing the catalytic performance of electrocatalysts. Currently, effective approaches to enhance the SMSI effect in supported electrocatalysts still need to be developed, and a comprehensive atomic-level understanding of the underlying reaction mechanisms remains unclear. In this study, a novel facet-junction strategy is proposed to enhance the SMSI between the loaded Ru atoms and the Co 3 O 4 support. By modulating the ratio of exposed facet for (111)/(100) crystal plane in Co 3 O 4 , the hydrogen evolution reaction (HER) performance can be dramatically enhanced by 560% and can achieve a Pt-like HER activity with the overpotential of 45 mV. Detailed analysis with atomic-resolution integrated differential phase contrast (iDPC)-scanning transmission electron microscopy (STEM), atomic-resolution high angle annular dark field (HADDF)-STEM, and electron energy loss spectroscopy (EELS) further proved that with proper (111)/(100) crystal plane ratio, the intensified charge distribution near the facet-junction region would modify the electronic structure around the active sites. This work provides new insights to enhance the SMSI and will contribute to the rational design of highly efficient electrocatalysts for water splitting.
研究领域:
材料科学
·
电催化
✓ 已验证
产品关联
DOI
高影响因子
CHINESE JOURNAL OF CHEMICAL ENGINEERING
·
2024
·
IF 3.7
Zhengjian Hou,Yuanyuan Zhu,Hua Chi,Li Zhao,Huijie Wei,Yanyan Xi,Lishuang Ma,Xiang Feng,Xufeng Lin
Tuning Strong Metal-support Interactions (SMSI) is a key strategy to obtain highly active catalysts, but conventional methods usually enable TiO x encapsulation of noble metal components to minimize the exposure of noble metals. This study demonstrates a catalyst preparation method to modulate a weak encapsulation of Pt metal nanoparticles (NPs) with the supported TiO 2 , achieving the moderate suppression of SMSI effects. The introduction of silica inhibits this encapsulation, as reflected in the characterization results such as XPS and HRTEM, while the Ti4 + to Ti3 + conversion due to SMSI can still be found on the support surface. Furthermore, the hydrogenation of cinnamaldehyde (CAL) as a probe reaction revealed that once this encapsulation behavior was suppressed, the adsorption capacity of the catalyst for small molecules like H 2 and CO was enhanced, which thereby improved the catalytic activity and facilitated the hydrogenation of CAL. Meanwhile, the introduction of SiO 2 also changed the surface structure of the catalyst, which inhibited the occurrence of the acetal reaction and improved the conversion efficiency of C=O and C=C hydrogenation. Systematic manipulation of SMSI formation and its consequence on the performance in catalytic hydrogenation reactions are discussed.
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
·
2019
·
IF 12.221
Jian Li,Yaping Lin,Xiulian Pan,Dengyun Miao,Ding Ding,Yi Cui,Jinhu Dong,Xinhe Bao
Strong metal–support interaction (SMSI) has been widely recognized for platinum-group metals on reducible oxide supports. Herein we report that the catalytic activity of Ni catalyst in CO2 methanation is significantly suppressed over conventional anatase (a-TiO2) support due to the SMSI-induced formation of a titania overlayer around the Ni nanoparticles. Furthermore, CO is the only product . In contrast, the NH3-treatment and H2-treatment of the a-TiO2 support enhance remarkably the activity of Ni, i.e., CO2 conversion increases by 1 order of magnitude and CO2 is hydrogenated almost exclusively to CH4. X-ray photoelectron spectroscopy (XPS), H2 and CO chemisorption, and low temperature electron paramagnetic resonance (EPR) reveal that the enhanced CO2 methanation activity may be related with the Ti3+ species in the bulk that are generated by reduction treatment, which likely have altered the SMSI between Ni and a-TiO2 support. This simple reduction treatment approach may be applicable to modulate the SMSI of other reducible oxide-supported metal catalysts.
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
Catalysts
·
2022
·Vol. 12
·期 10
·1286
·
IF 4.501
Ravi Balaga,Kishore Ramineni,Xiaoqiang Zhang,Peifang Yan,Mahender Reddy Marri,Vijayanand Perupogu,Zongchao Conrad Zhang
Conversion of biomass-derived furfural (FFA) platform molecule to value-added tetrahydrofurfuryl alcohol (THFA) molecule is a sustainable route using an efficient non-noble metallic catalyst in water solvent. In this work, Ni in various loadings on mesoporous titanium dioxide (m-TiO2) was synthesized in one pot by Evaporation-Induced Self-Assembly (EISA). The synthesised catalysts were evaluated for the hydrogenation of furfural to tetrahydrofurfuryl alcohol. The catalysts were characterised using a combination of spectroscopic techniques such as XRD, H2-TPR, H2-TPD, XPS, SEM-EDX, TEM, and HR-TEM. The characterization results show that the Ni/m-TiO2materials exhibit enhanced electron-rich active sites, facilitated hydrogen spillover, uniform dispersion of small Ni particles (~5 nm), and strong metal support interaction between Ni and TiO2. Among the various Ni dopings, 7.5 wt.% Ni/m-TiO2catalyst exhibited the best performance and achieved 99.9% FFA conversion and 93.2% THFA selectivity in water solvent at 100 °C and under 2 MPa H2. Additionally, detailed kinetic studies, process parameters, the stability and reusability of the catalyst were also studied. The results demonstrated that the 7.5 wt.% Ni/m-TiO2catalyst is highly active and stable.Keywords:biomass;furfural hydrogenation;electron-rich Ni;SMSI;spillover
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
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Zequn Zhang,Yuan Shu,Qian Liu,Shuxian Bi,Pengfei Zhang
Colloidal nanoparticles with uniform particle size distribution, tailored exposed facets, and controllable compositions appealed to broad interests in heterogeneous catalysis. Nevertheless, due to the strong attachment of capping agents to the nanoparticles, cleaning the nanoparticle surface without changing the size of nanoparticles remains a significant challenge. Herein, based on the double confinement of the strong metal-support interaction (SMSI) effect and carbon encapsulation, the well-stabilized Ni-ZnO-S3 catalyst was successfully synthesized. The size of Ni nanoparticles after calcination in the sequence of H 2 -N 2 mixture, air, and H 2 -N 2 mixture remained below 5 nm. Due to no significant size change in Ni nanoparticles, the prepared Ni-ZnO-S3 catalyst served well as model catalysts in the RWGS reaction, where the CO 2 conversion and CO yield increased proportionally to the Ni loading weight. According to the result of in-situ FTIR, an associative mechanism of RWGS reaction over Ni-ZnO-S3 was also identified. Therefore, this dual protect strategy provides a potential solution for building highly anti-sintering catalysts based on the colloidal synthesis route.
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 A-GENERAL
·
2025
·
IF 4.8
Qingting Zhang,Yongbin Wu,Abouelhassan A. Gomaa,Andreas Goldbach
Supported Au catalysts are widely investigated for selective oxidation processes. Here, propylene oxidation was studied over Au nanoparticles supported on MoO 3 nanobelts. Intriguingly, the Au particles were encapsulated by MoO x layers in oxidizing atmospheres yielding Au@MoO x aggregates which signal non-classical oxidative strong metal-support interaction (SMSI) between Au and MoO 3 . The core@shell particles enhanced the acrolein selectivity of MoO 3 from 18 % up to 81 % while its formation rate accelerated more than twentyfold to 1153 µmol g cat −1 h −1 at 3 wt% Au loading and 350 °C. In situ CO DRIFTS measurements, H 2 -TPR and XPS analyses suggest that the Au@MoO x entities facilitate the transfer of MoO 3 lattice oxygen to propylene in line with the Mars-van Krevelen mechanism for acrolein formation. Apparent activation energies in the 113–163 kJ mol −1 range point to re-oxidation of the ensuing oxygen-deficient MoO x moieties as rate-limiting acrolein formation step. Consequently, the oxidative SMSI strongly promotes propylene conversion to acrolein over MoO 3 -supported Au catalysts.
研究领域:
催化化学
·
材料科学
·
表面科学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Energy Materials
·
2024
·Vol. 15
·期 3
·2402295
·
IF 24.4
Songshan Zhu,Shimin Ma,Di Song,Sufang He,Yunzhu Wang,Jichang Lu,Tianhao Ai,Yongming Luo
The regulation and stabilization of strong metal-support interactions (SMSI) in high temperature hydrogen-rich reaction condition remains a huge challenge due to its structural sensitivity. Herein, tunable SMSI is constructed and stabilized on TiO 2 supported Ni catalysts by TiO 2 crystal phase engineering strategy, and then a SMSI-degree-depended ethanol stream reforming (ESR) performance is demonstrated. Rutile supported Ni exhibited a weakened SMSI with 48.6% coverage, exposing more metallic Ni and Ni-TiO 2 perimeter interface sites, and displayed exceptional H 2 yield of 4.7 mol H2 /mol ethanol and an ultra-long stability of 420 h without deactivation at 500 °C. The low reaction energy and high resistance to carbon deposition (0.9 mg c /g cat ·h) and Ni 0 sintering on Ni/r-TiO 2 catalyst explained its excellent catalytic performance. Furthermore, the effect of well-defined SMSI structures on the reaction pathway and deactivation mechanism of the ESR is clarified. This work provides a precedent for the tailor and application of SMSI in high temperature hydrogen-rich reaction conditions.
研究领域:
催化化学
·
材料科学
·
能源化学
✓ 已验证
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2021
·
IF 8.128
Zhi Hu,Zidan Zou,Aidi Xie,Chun Chen,Xiaoguang Zhu,Yunxia Zhang,Haimin Zhang,Huijun Zhao,Guozhong Wang
Ceria has been widely used as catalyst support displaying a size- or shape-dependent catalytic performance due to the strong metal-support interaction (SMSI) effect with active metal. Almost all the studies on the SMSI effect of ceria-supported metal catalysts are involved generally in gas-phase reaction, but rarely in the liquid-phase reaction system. In this work, Cu/CeO 2 -P (copper loaded on nano-polyhedral CeO 2 with (1 1 1) terminated surface) was investigated its catalytic performance on liquid-phase hydrogenation and studied the SMSI effect by comparing with the catalysts supported on nano-rod and nano-cube CeO 2 . It was found that Cu was highly dispersed on the external surface of ceria in the Cu/CeO 2 -P catalyst via a moderate SMSI effect. Furthermore, the degree of the interaction showed great influence on the chemical state of Cu species, and the ratio of (Cu + +Cu 0 )/Cu 2+ in Cu/CeO 2 -P was higher than Cu/CeO 2 -R (Cu loaded on nano-rod CeO 2 with (1 1 0) plane) and Cu/CeO 2 -C (Cu loaded on nano-cube CeO 2 with (1 0 0) facet). As a result, the Cu/CeO 2 -P catalyst showed the best catalytic performance among three types of catalysts. Based on series of catalytic investigations, the catalytic performance in liquid-phase hydrogenation was intrinsically relevant to the crystal plane effect and reduced Cu proportion induced by an appropriate SMSI effect, which was completely different from gas-phase hydrogenation.
研究领域:
催化化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
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