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
Cell Discovery
·
2021
·Vol. 7
·期 1
·1-12
·
IF 10.849
Meng Wensi,Zhang Lijie,Cao Menghao,Zhang Yongjia,Zhang Yipeng,Li Ping,Kang Zhaoqi,Guo Shiting,Xu Ping,Ma Cuiqing,Gao Chao
Overflow metabolism-caused acetate accumulation is a major problem that restricts industrial applications of various bacteria. 2,3-Butanediol (2,3-BD) synthesis in microorganisms is an ancient metabolic process with unidentified functions. We demonstrate here that acetate increases and then decreases during the growth of a bacterium Enterobacter cloacae subsp. dissolvens SDM. Both bifunctional acetaldehyde/ethanol dehydrogenase AdhE-catalyzed ethanol production and acetate-induced 2,3-BD biosynthesis are indispensable for the elimination of acetate generated during overflow metabolism. 2,3-BD biosynthesis from glucose supplies NADH required for acetate elimination via AdhE-catalyzed ethanol production. The coupling strategy involving 2,3-BD biosynthesis and ethanol production is widely distributed in bacteria and is important for toxic acetate elimination. Finally, we realized the co-production of ethanol and acetoin from chitin, the second most abundant natural biopolymer whose catabolism involves inevitable acetate production through the coupling acetate elimination strategy. The synthesis of a non-toxic chemical such as 2,3-BD may be viewed as a unique overflow metabolism with desirable metabolic functions.
研究领域:
微生物学
·
代谢工程
✓ 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
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催化材料
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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
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生物质转化
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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
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催化材料
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理论计算
✓ 已验证
产品关联
DOI
高影响因子
Nature Nanotechnology
·
2020
·Vol. 15
·期 10
·848-853
·
IF 31.538
Jiang Lizhi,Liu Kunlong,Hung Sung-Fu,Zhou Lingyun,Qin Ruixuan,Zhang Qinghua,Liu Pengxin,Gu Lin,Chen Hao Ming,Fu Gang,Zheng Nanfeng
Hydrogen spillover is a well-known phenomenon in heterogeneous catalysis; it involves H 2 cleavage on an active metal followed by the migration of dissociated H species over an ‘inert’ support 1 , 2 , 3 , 4 , 5 . Although catalytic hydrogenation using the spilled H species, namely, spillover hydrogenation, has long been proposed, very limited knowledge has been obtained about what kind of support structure is required to achieve spillover hydrogenation 1 , 5 . By dispersing Pd atoms onto Cu nanomaterials with different exposed facets, Cu(111) and Cu(100), we demonstrate in this work that while the hydrogen spillover from Pd to Cu is facet independent, the spillover hydrogenation only occurs on Pd 1 /Cu(100), where the hydrogen atoms spilled from Pd are readily utilized for the semi-hydrogenation of alkynes. This work thus helps to create an effective method for fabricating cost-effective nanocatalysts with an extremely low Pd loading, at the level of 50 ppm, toward the semi-hydrogenation of a broad range of alkynes with extremely high activity and selectivity.
研究领域:
催化
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材料科学
·
化学工程
✓ 已验证
DOI
PubMed
高影响因子
Particuology
·
2024
·
IF 4.1
Jingchuan Wang,Junhong Luo,Yong Yao,Jiangfeng Song,Yan Shi
To improve room-temperature hydrogen storage, palladium (Pd) nanoparticles were innovatively decorated by carbon bridge onto the amino-group functioned Zr-terephthalate metal-organic framework (MOF) UiO-66 to reduce the diffusion energy barrier and then improve the hydrogen spillover effect. Powder X-ray diffraction shows broad Pd peak and retained UiO-66-NH 2 integrity after Pd decoration. The hydrogen uptake capacity show that UiO-66-NH 2 -Pd exhibits best hydrogen storage performance than UiO-66-NH 2 and pristine UiO-66. The hydrogen up taken in Pd decorated UiO-66 (UiO-66-NH 2 -1Pd) was close to 4 wt% under 20 MPa at room temperature. Density functional theory (DFT) calculations show that hydrogen adsorption energy of UiO-66-NH 2 -Pd was −0.5897 eV, which was much lower than that of UiO-66-NH 2 (−0.3716 eV) and UiO-66 (−0.2975 eV). Ultimately, Pd decorated NH 2 group functioned UiO-66 enable improve storage capacities through hydrogen spillover under ambient conditions which could satisfy the demand for sustainable energy, especially for the long-term storage energy media.
研究领域:
材料科学
·
能源科学
✓ 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
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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
危险品化学品经营许可证（带存储）