JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Juan Du,Tianfeng Cai,Qiao Han,Hongda Wu,Qing Zhao,Lufan Zheng,Shuo Liu,Zhanxu Yang
The hydrogen spillover is considered a powerful strategy for improving the kinetics of hydrogen evolution reaction (HER) due to the decoupling of hydrogen adsorption and desorption. However, the hydrogen spillover rate strongly depends on the metal-support interfaces, and the Fermi levels (E f ) difference between metal and support hinders the occurrence of hydrogen spillover. Here, we prepared platinum (Pt) doped on molybdenum disulfide (MoS 2 ) with sulfur vacancies (Sv) catalyst (Pt/Sv-MoS 2 ) and investigated the internal relationship between metal-support interfaces and hydrogen spillover mechanism. The experimental and theoretical results show that sulfur (S) vacancies reduce the work function (ΔΦ) at the metal-support interface, thus accelerating the migration rate of hydrogen from Pt to Sv-MoS 2 . Meanwhile, the introduction of S vacancies promotes the high dispersion of Pt nanoparticles (Pt NPs) and weakens the electron supply from Pt to MoS 2 , facilitating active hydrogen (*H) adsorption step and thus increasing the hydrogen coverage on the Pt sites. Consequently, the prepared Pt/Sv-MoS 2 catalyst exhibited significantly enhanced HER activity, achieving an overpotential of 26 mV at 10 mA·cm −2 and a Tafel slope of only 28 mV·dec −1 , which is superior to commercial 20 % Pt/C.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Small
·
2024
·Vol. 21
·期 1
·2406022
·
IF 13
Jiamin Zhao,Meimei Kou,Qing Yuan,Ying Yuan,Jinsheng Zhao
Tungsten carbide (WC x ) is a promising alternative to platinum catalysts for hydrogen evolution reaction (HER). However, strong tungsten–hydrogen bond hinders hydrogen desorption while favoring H + reduction, thus limiting HER kinetics. Inspired by the phenomenon of hydrogen spillover in heterogeneous catalysis, a ruthenium (Ru) doped-driven activated hydrogen migration from WC x surface to Ru is reported. This approach achieved high activity with an ultralow overpotential of 9.0 mV at 10 mA·cm −2 and superior stability at an industrial-grade current density of 1.0 A·cm −2 @ 1.65 V. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and operando electrochemical impedance spectra revealed that this exceptional hydrogen production—which surpasses that of previously reported Pt/C catalysts—is attributable to the outstanding ability of WC x to induce water dissociation and hydrogen spillover from WC x to Ru surface. During the HER process, the rigid interfacial water network negatively affected the HER efficiency under alkaline conditions. The WC x sites disrupted this rigid structure, facilitating the contact between activated hydrogen (H * ) and WC x sites. Subsequently, H * migrates to Ru surface, where hydrogen recombination occurs to produce H 2 . This work paves a new avenue for the construction of coupled catalysts at the atomic scale to facilitate HER electrocatalysis.
研究领域:
电化学
·
催化材料
·
能源科学
✓ 已验证
DOI
高影响因子
Molecular Catalysis
·
2024
·
IF 3.9
Zhe Zhang,Jianan Zhang,Shuai Chen,Yanan Liu,Yufei He,Dianqing Li
Hydrogen spillover phenomenon can significantly impact the activity in hydrogenation reaction, but the spillover is limited in a very short range on non-reducible Al 2 O 3 , a most widely used industrial support. Herein, Al 2 O 3 doped with different lanthanides (ln) was prepared by co-precipitation, which was then used to produce Pd/ln-Al 2 O 3 catalysts. These catalysts display much higher hydrogenation activity towards alkylated anthraquinone than undoped Pd/Al 2 O 3 catalyst and those modified by non-lanthanide elements. After the introduction of lanthanides, the reaction order of H 2 decreases from 1 to 0. Further characterization and DFT calculation show that H 2 storage ability is increased for ln-doped catalysts due to the low activation energy of H transfer and low adsorption energy of H on O(-ln) sites. In addition, a reasonable relationship between reducibility of ln 3+ in catalysts and the catalytic performance is found.
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
MICROPOROUS AND MESOPOROUS MATERIALS
·
2023
·
IF 5.2
Pai Peng,Yaning Yue,Mengxi Han,Jun Shi,Jing Yang,Junwen Chen,Qiang Chen
Design of heterogeneous catalyst to achieve efficient conversion of biomass to high added-value chemicals is still very attractive. Herein, taking industrially important selective hydrogenation of furfural to furfuryl alcohol as an example, the designed amorphized HA zeolite encapsulation of platinum clusters (denoted as Pt@HA) exhibited excellent catalytic selectivity at totally conversion of the reactant furfural, along with good reusability and poison resistance ability. The selected amorphized HA zeolite with very small pore size constrained the reactant furfural to be reacted through hydrogen spillover process at zeolite surface, instead of to be adsorbed and activated onto Pt surface. Resulting from the stronger interaction between nucleophilic oxygen atom of aldehyde group and acid site at HA zeolite surface than that of furan ring group, furfural preferred to adsorb onto Pt@HA surface with the end of aldehyde group rather than the end of furan ring group, thus facilitating the spilled H atom to react with aldehyde group to give desired furfuryl alcohol product exclusively.
研究领域:
催化化学
·
生物质转化
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Xu Yu,Han Tian,Zhengqian Fu,Fenglai Pei,Lingxin Peng,Ge Meng,Fantao Kong,Yafeng Chen,Chang Chen,Ziwei Chang,Xiangzhi Cui,Jianlin Shi
The hydrogen spillover effect on metal-supported electrocatalysts is of great significance in hydrogen-involved reactions, especially in a hydrogen oxidation reaction (HOR). Herein, a facile thermal reduction method has been adopted to synthesize W18O49 (WO2.72) nanospheres decorated with single nickel atoms, and the obtained Ni-WO2.72-T (1.20 wt % Ni) was used as a probe catalyst for investigating the hydrogen spillover effect, which exhibits enhanced HOR performance, stability, and resistance to CO poisoning in acidic electrolytes. Based on in situ Raman spectroscopy and the density functional theory (DFT) calculation, a synergistic effect between Ni single-atom active sites and the hydrogen spillover effect is proposed to contribute to the HOR performance on Ni-WO2.72-T. Briefly, the introduction of single Ni atoms induces electron redistribution on Ni-WO2.72-T, making Ni atoms positively charged for H2 adsorption and activation, and on the other hand, the reversible phase transformation between WO2.72 and HxWO2.72 facilitates H* transfer from Ni to WO2.72, i.e., hydrogen spillover, resulting in elevating the HOR catalytic activity. Both experimentation and theoretical calculations demonstrate that the reversible phase transformation of the WO2.72 substrate strengthens the hydrogen spillover effect and thus elevates the HOR catalytic performance, which is believed to be helpful in designing highly active catalysts for hydrogen-involving reactions.
研究领域:
电化学
·
催化材料
·
理论计算
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Kairui Liu,Peifang Yan,Hong Jiang,Zhi Xia,Zhanwei Xu,Shi Bai,Z. Conrad Zhang
Selective hydrocleavage of aromatic C O bond while preserving the aromatic ring is a desired catalytic process in hydrodeoxygenation (HDO) of biomass derived aromatic oxygenates to high value biochemicals. Guaiacol with typical methoxy and phenolic hydroxyl groups is a representative aromatic di-oxygenates of lignin fragments. Sub-nanometer sized silver, a poor hydrogenation metal catalyst, was found to initiate H 2 dissociation and H spillover onto anatase TiO 2 (TiO 2 -A) surface. The spillover hydrogen enhanced the partial reduction of TiO 2 -A surface at a substantially lowered temperature as compared to the reduction of TiO 2 -A by molecular H 2 . The reduction of TiO 2 -A surface by spillover hydrogen was enhanced at Ag loading as low as 0.01 wt% on TiO 2 -A. The ratio of spillover H to Ag was as high as 675 at Ag loading of 0.01 wt% and the ratio decreased with increasing Ag loading. We found that the yield of phenolic products was linearly correlated with the amount of spillover hydrogen that created oxygen vacancy (Ov) through partial reduction of TiO 2 -A surface. Methanol was formed as the main side-product, indicating that the direct hydrocleavage of aromatic C-OCH 3 in guaiacol is favored over that of aromatic C-OH on the created site.
研究领域:
催化化学
·
生物质能
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Lulu Zhang,Rui Li,Luyao Cui,Zijun Sun,Lijun Guo,Xiaochao Zhang,Yunfang Wang,Yawen Wang,Zhuobin Yu,Tao Lei,Xuan Jian,Xiaoming Gao,Caimei Fan,Jianxin Liu
Synergistic water activation and nitrogen reduction process is significant to the photocatalytic ammonia synthesis reaction, in which the obtainment of active hydrogen (H*) from H 2 O dissociation and then transfer to N 2 activation site is essential. Herein, the oxygen vacancies (OVs) enhanced hydrogen spillover is used to increase the H* transfer between the H 2 O activation site (Ru) and the N 2 activation site (OVs-rich W 18 O 49 ). Results shown that the OVs-rich Ru/W 18 O 49 achieves high activity for NH 3 production with a yield of 222.75 µmol‧g −1 ‧h −1 , which is 5.60 folds of the OVs-deficient Ru/W 18 O 49 . Control experiments, characterization, and theoretical calculation made it clear that OVs played crucial roles in enhancing the hydrogen spillover by modifying the support's Gibbs free energy for hydrogen adsorption and lowering the barrier of H* migration. Finally, the detail mechanism was explained from a new perspective. This strategy may provide new insights for other hydrogenation reactions under mild conditions.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
AICHE JOURNAL
·
2023
·Vol. 69
·期 7
·e18078
·
IF 3.7
Yanping Yang,Jiarui Yang,Shucheng Shi,Yunhong Luo,Xingjun Xu,Yanan Liu,Dianqing Li,Junting Feng
Selective acetylene hydrogenation is a strongly exothermic process, easy to cause coking and metal agglomeration, and thus leads to deactivation. In this work, Pd/TiO 2 with different oxygen vacancies (V o ) were synthesized by controlling reduction temperature in 300–700°C, in which Pd/TiO 2 -HT300 (HT is reduction temperature) possessed the highest V o content. It was found highly dispersed Pd nanoparticles adjacent to more V o exhibited enhanced catalytic behavior (near 100% conversion at 55°C with 80% selectivity and turnover frequency of 0.12 s −1 ) due to hydrogen spillover generation and electron donation originating from V o sites, confirmed by in situ x-ray photoelectron spectroscopy, in situ Raman, and H 2 -temperature programmed desorption. More importantly, the increasing V o sites trap the released heat and devote to a decrease of heat accumulation over a single active Pd site, and consequently inhibit Pd agglomeration and polymerization, affirmed by high-resolution transmission electron microscopy, CO chemisorption, and thermogravimetric analysis.
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
·
2025
·
IF 13.1
Fan Gao,Wen-Gang Cui,Xinqiang Wang,Zhenglong Li,Yongchang Chen,Zichao Shen,Ke Wang,Yong Gao,Jian Miao,Yaxiong Yang,Jian Chen,Shaohua Shen,Hongge Pan
Hydrogen spillover has been believed to play an essential role in the reaction path in photocatalysis, yet its rational regulation remains a considerable challenge for the design of highly efficient photocatalysts. Herein, hydrogen spillover can be well regulated at ZnIn2S4 with surface decorated by cubic α-MoC1–x quantum dots (QDs) with different lattice strain (ZIS/QDs). With the increasing lattice strain of α-MoC1–x, the composite shows first increased and then decreased photocatalytic hydrogen evolution (PHE). Spectroscopic characterizations and calculation analysis indicate that PHE performance of ZIS/QDs is highly corelated with hydrogen spillover rather than charge transfer process. Further systematic investigations suggest that compressive lattice strain uplifts the Fermi level of α-MoC1–x and optimizes the interfacial spillover barrier between α-MoC1–x and ZnIn2S4, achieving well-manipulated hydrogen spillover and enhanced PHE performance. This work demonstrates a general design from the perspective of lattice strain to harness hydrogen spillover effect in heterogeneous interface for hydrogen generation.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
FUEL
·
2024
·
IF 6.7
Zhaozhuo Yu,Wenzhuo Kong,Yaping Guo,Wen Liang,Jiawei Liang,Meijuan Chen,Dongxu Zhao,Hongzhen Ma,Xiangjun Liu,Solomon Inalegwu Okopi,Lei Che,Qi Zhang,Zhuohua Sun,Fuqing Xu
Eco-friendly lignin depolymerization into monomeric phenols in an aqueous system is essential for the sustainable and green valorization of lignocellulosic biomass. However, a major challenge in this process is the development of efficient and stable catalysts for aqueous reductive catalytic fractionation (RCF), as water can cause catalyst deactivation and reduce monomer yields. In this study, a water-resistant RuNiZnO x /Nb 2 O 5 catalyst is developed that demonstrates excellent catalytic activity and stability in aqueous systems, achieving a near-theoretical monomeric phenol yield of 40.1 wt% under reaction conditions of 240℃ and 3 MPa H 2 for 4 h. The excellent performance of this catalyst is attributed to the synergistic hydrogen spillover effect between Ni and Ru and the strong acidic properties of ZnO, as revealed by in-situ XPS analysis and NH 3 -TPD, respectively. This hydrogen spillover effect significantly alters the product composition, promoting the generation of POH-S/G from lignin model compounds. Additionally, screening of the catalyst support materials revealed that Nb 2 O 5 not only enhances Ru dispersion but also improves its stability, resulting in a minor decrease in lignin monomer yield observed after three cycles.
研究领域:
生物质化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF ENERGY RESEARCH
·
2019
·Vol. 43
·期 8
·3284-3294
·
IF 3.343
Xiaoyang Wan,Xuefeng Wei,Juan Miao,Ruichang Zhang,Jun Zhang,Qingshan Jason Niu
Summary A wide compositional range of Pd-Ni/Cd on polypyrrole (PPy)-modified Ti plates (Pd-Ni/Cd/PPy/Ti) was fabricated via electrochemical deposition. The hydrogen absorption properties of the prepared Pd-Ni/Cd/PPy/Ti electrodes were evaluated using cyclic voltammetry and chronoamperometry in acidic media. The optimal Pd 36 -Ni 7 /Cd 57 /PPy/Ti electrode achieved a hydrogen storage capacity of 331.3 mC cm −2 mg −1 and an H/Pd ratio of 0.77. The enhancement of the hydrogen storage was attributed to a synergistic effect between the Pd-Ni/Cd catalysts. The surface morphology, crystallinity, and chemical composition of the Pd-Ni/Cd/PPy/Ti electrode were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), respectively. Hydrogen spillover occurred on the trimetallic catalysts, and secondary hydrogen spillover occurred on the PPy/Ti support. The enhanced hydrogen sorption capacity was due to both the synergistic effect of the trimetallic catalysts and the assistance of PPy, making Pd-Ni/Cd/PPy/Ti a promising hydrogen storage material.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Yibo Qin,Longfei Chen,Lixia Ge,Yanfeng Zhu,Wanting Li,Xinxin Cao,Tianchang Wang,Jiong Li,Wei Han,Xinqing Chen
Hydrogen spillover plays a crucial role in heterogeneous catalysis, significantly enhancing the activity of catalysts. However, the promotion mechanism of hydrogen spillover on non-reducible oxide supports (such as zeolite) is rarely reported. Herein, we prepared Ru@Beta sample by in-situ approach, effectively encapsulating Ru species into Beta zeolite. Additionally, three samples (Ru/SiO 2 , Ru@Naβ, and Ru@Hβ) with different hydrogen spillover effect were prepared. The optimal concentration of Ru was 0.5 wt%, and the Ru@Hβ sample with the strongest hydrogen spillover has 100 % conversion rate of N-ethylcarbazole (NEC) and 98 % selectivity towards to 12H-NEC. In contrast, the Ru/SiO 2 with weak hydrogen spillover has only 89.5 % conversion rate and 28.9 % selectivity of 12H-NEC. Notably, the Ru@Hβ can still completely convert NEC even after 7 cycles, thereby exhibiting its remarkable activity and stability. Various characterizations (HAADF-STEM, XPS, EXAFS, in-situ DRIFT, and H 2 -TPD) indicate the superior catalytic performance of Ru@Hβ with strong hydrogen spillover effect, originating from the presence of more hydroxyl (–OH) and Brønsted acid on the surface, while Lewis acid act as hydrogen acceptors and NEC hydrogenation sites. This work not only expands our understanding of the hydrogen spillover, but also paves the way onto the potential applications in heterogeneous catalysis for efficient hydrogenation.
研究领域:
催化化学
·
材料科学
·
能源存储
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）