Industrial Chemistry & Materials
·
2024
·
IF 0
Huige Chen,Zhenhua Li,Chao Zhou,Run Shi,Tierui Zhang
The exothermic characteristic of the water-gas-shift (WGS) reaction, coupled with the thermodynamic constraints at elevated temperatures, has spurred a research inclination towards conducting the WGS reaction at reduced temperatures. Nonetheless, the challenge of achieving efficient mass transfer between gaseous CO and liquid H2O at the photocatalytic interface under mild reaction conditions hinders the advancement of the photocatalytic WGS reaction. In this study, we introduce a gas–liquid–solid triphase photocatalytic WGS reaction system. This system facilitates swift transportation of gaseous CO to the photocatalyst's surface while ensuring a consistent water supply. Among various metal-loaded TiO2 photocatalysts, Rh/TiO2 nanoparticles positioned at the triphase interface demonstrated an impressive H2 production rate of 27.60 mmol g−1 h−1. This rate is roughly 2 and 10 times greater than that observed in the liquid–solid and gas–solid diphase systems. Additionally, finite element simulations indicate that the concentrations of CO and H2O at the gas–liquid–solid interface remain stable. This suggests that the triphase interface establishes a conducive microenvironment with sufficient CO and H2O supply to the surface of photocatalysts. These insights offer a foundational approach to enhance the interfacial mass transfer of gaseous CO and liquid H2O, thereby optimizing the photocatalytic WGS reaction's efficiency.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
DOI
Catalysts
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2020
·Vol. 10
·期 12
·1379
·
IF 3.52
He Liu,Shiguang Fan,Xu Gong,Jian Wang,Aijun Guo,Kun Chen,Zongxian Wang
Partial hydrogenation of anthracene under CO-H2O, N2-H2O, and H2-H2O over Fe-based catalysts was studied at 400 °C and 10 MPa. Results show that the Fe-based catalysts display obvious catalytic activity for anthracene hydrogenation under CO-H2O instead of hydrogenation under N2-H2O and H2-H2O. The activity follows in the order of Fe(NO3)3·9H2O > Fe naphthenate > FeSO4·7H2O. Even though the amount of molecular hydrogen remains higher than that of in situ hydrogen, the anthracene conversion with in situ hydrogen is remarkably higher. It demonstrates that the in situ hydrogen is more active than molecular hydrogen for PAH hydrogenation. To further reveal the exact fate of these Fe-based catalysts, the decomposed products under CO-H2O, N2-H2O and H2-H2O were characterized by TG, XRD, and TEM. Results indicate that the Fe3O4species play a key role in hydrogenation of anthracene under CO and H2O. Higher catalytic activity for Fe(NO3)3·9H2O is due to its complete decomposition at 350 °C to acquire higher concentration of active Fe3O4species. The possible form of in situ hydrogen during this process is also discussed. Given that heavy oil contains abundant polyaromatics, these results are meaningful for enhancing hydrogen shuttling to heavy oil by producing natural hydrogen donors and, thus, benefiting the high-efficient upgrading.Keywords:PAH hydrogenation;in situ hydrogen;water gas shift reaction;natural hydrogen donors
研究领域:
化学工程
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
·
IF 21.1
Hui Zhao,Xin-Pu Fu,Wei-Wei Wang,Jin-Cheng Liu,Chun-Jiang Jia
Despite the supported Au demonstrating superior activity in catalyzing various reactions, their stubborn and widespread deactivation issue has long remained unsolved. Therefore, the challenge in current investigations of Au-based catalysts could be divided into two aspects: uncovering the authentic molecular induction for the deactivated evolution and fabricating interfacial structures combining efficiency and stability. In this work, by incorporating NiO x (H) adjacent to small active Au 1 /Au n species, the as-formed 0.5Au-5NiO x (H)/CeO 2 catalyst simultaneously achieved high reactivity ( r = 5.23 mmol CO ·g Au −1 ·s −1 ) toward the water-gas shift (WGS) reaction and remarkable long-term stability with time-on-stream of 100 h at 250 °C, significantly surpassing the reference Au/CeO 2 counterpart as well as the other oxides-supported Au catalysts reported previously. Comprehensive in-situ characterizations and DFT calculations revealed that the CO molecules, rather than H 2 , H 2 O, or CO 2 molecules, are the dominant molecular driver for Au aggregation, correspondingly inducing the degraded catalytic efficiency. Specifically, on the one hand, the strong CO−Au coordination degraded the ejection barrier of Au atoms from Au-Au coordination; on the other hand, the −OH groups as intermediates from H 2 O dissociation, participating in the stabilization of Au species upon the surface, were dynamically consumed by CO molecules. For these regards, the adjacent Ni adatoms promote the sufficient generation of stable −OH groups for stabilizing Au atoms under WGS reaction. As a result, the corresponding Au−Au ejection and Au−O diffusion barriers of as-formed Au n −O(H)−Ni/CeO 2 combinations are significantly enlarged, which thereby boosts the structural stability in the CO-containing atmospheres.
研究领域:
催化化学
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材料化学
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表面科学
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物理化学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2019
·
IF 6.97
Yanpeng Chen,Xing Zhu,Kongzhai Li,Yonggang Wei,Yane Zheng,Hua Wang
Syngas generation via thermochemical H2O–CO2 splitting relies heavily on a high-temperature decomposition of metal oxides into a reduced state. Meanwhile, typical chemical looping partial oxidation of methane to syngas suffers from the carbon deposition and the low selectivity toward syngas. To overcome these drawbacks, the partial oxidation of methane and H2O–CO2 splitting are coupled to consist of an alternative chemical looping redox scheme for the generation of Fischer–Tropsch (F–T)-ready syngas. The usability of lattice oxygen in a redox catalyst is facilitated, and its redox property is also thermodynamically optimized by using H2O and CO2 as soft oxidants, guaranteeing an effective generation of syngas from both redox steps. The carbon tolerance is greatly enhanced due to H2O or CO2 gasification in the reoxidization step. Experimental studies confirm the redox scheme by using CeO2–LaFeO3 redox catalyst, demonstrating generation of syngas with an H2/CO molar ratio around 2.0 in both methane partial oxidation and H2O–CO2 splitting steps over 30 repeated cycles at 850 °C. A syngas selectivity of 95% in methane partial oxidation and nearly 100% conversion of CO2 to CO can be achieved. Synergistic effect and competing reaction between H2O and CO2 splittings over the reduced redox catalyst are the key factors for the control of syngas composition and the intensification of CO2 splitting. The proposed approach can potentially be applied for production of F–T-ready syngas with an increased yield without the need for gas separation when compared to the state-of-the-art thermochemical splitting or methane chemical looping partial oxidation processes.
研究领域:
能源科学
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化学工程
✓ 已验证
DOI
高影响因子
Applications in Energy and Combustion Science
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2025
·
IF 6
Zongqiang Ren,Zhenghui Gao,Zhenliang Guo,Peiwen Liu,Dingding Yao
Thermo-chemical conversion of waste plastics offers a sustainable strategy for integrated waste management and clean energy generation. To address the challenges of low gas yield and rapid catalyst deactivation due to coking in conventional gasification processes, an innovative three-stage chemical looping gasification (CLG) system specifically designed for enhanced hydrogen-rich syngas production was proposed in this work. A comparative analysis between conventional gasification and the staged CLG system were firstly conducted, coupled with online gas analysis for mechanistic elucidation. The influence of Fe/Al molar ratios in oxygen carriers and their cyclic stability were systematically examined through multicycle experiments. Results showed that the three-stage CLG in the presence of Fe1Al2 demonstrated exceptional performance, achieving 95.23 mmol/g plastic of H 2 and 129.89 mmol/g plastic of syngas respectively, representing 1.32-fold enhancement over conventional method. And the increased H 2 /CO ratio (2.68-2.75) reflected better syngas quality via water-gas shift. Remarkably, the oxygen carrier maintained nearly 100% of its initial activity after 7 redox cycles, attributed to the incorporation of Al 2 O 3 effectively mitigating sintering and phase segregation through metal-support interactions. These findings establish a three-stage CLG configuration with Fe-Al oxygen carriers as an efficient platform for efficient hydrogen production from waste plastics, contributing to sustainable waste valorisation and carbon-neutral energy systems.
研究领域:
能源化学工程
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环境科学与技术
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材料科学与工程
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催化化学
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资源循环利用
✓ 已验证
DOI
高影响因子
ACS Catalysis
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2022
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IF 13.7
Shuangxi Lin,Qiang Wang,Maoshuai Li,Ziwen Hao,Yutong Pan,Xiaoyu Han,Xiao Chang,Shouying Huang,Zhenhua Li,Xinbin Ma
Controlling the selectivity of CO2 hydrogenation by catalysis is a fundamental challenge. This study examines the interrelation between active sites and reaction pathways in Ni-catalyzed CO2 hydrogenation. The alloying of Ni with Zn to charged (Niσ––Znσ+) active sites modifies the electronic structure and d-band center, weakens the interaction with CO/H2, and preferentially catalyzes the reverse water gas shift to CO with the thermodynamically favored methanation pathway switched off. The charged dual sites can stabilize the activated CO2 species in a η2(C, O) bridge configuration, directly dissociate the C═O bond to *CO, and promote CO desorption. The mechanistic investigation has elucidated the reaction pathways in the Ni-catalyzed CO2 hydrogenation and identified the crucial intermediates that impacted the product selectivity, which can provide a theoretical guide for the Ni-based catalyst design.
研究领域:
催化化学
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材料科学
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表面科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Zhiyang Yu,Yuqi Shao,Wenyao Li,Yongzhuo Liu
Integrated CO2 capture and conversion (ICCC), which simultaneously achieves CO2 enrichment and in situ conversion, represents a promising strategy for reducing CO2 emissions. Dual-function materials (DFMs) that exhibit stable and highly efficient adsorption and catalytic conversion properties are essential to the success of this strategy. In this study, we developed novel Mo/Fe-doped CaO-based DFMs for the integrated CO2 capture and reverse water–gas shift (ICCC–RWGS) process. The synthesized DFMs was evaluated through adsorption–conversion cyclic experiments in a fixed-bed reactor, complemented by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM) mapping, and X-ray photoelectron spectroscopy (XPS) characterizations. The results indicate that the generated composites with a specialized structure not only provide stable support for CaO but also regulate the RWGS process. Specifically, the formation of Ca2Fe2O5 facilitates the hydrogenation of CaCO3 via redox reactions, while the generation of CaMoO4 and Ca2FeMoO6 alleviates both the volume-change effects of CaO caused by CO2 adsorption–hydrogenation cycles and the carbon deposition side reactions caused by Fe. DFMs with a Mo/Fe mass ratio of 1:9 exhibited a CO2 capture capacity of 14.8 mmol/g DFM, a CO yield of 11.4 mmol/g DFM, and good cyclic properties at 650 °C, making it a promising DFM for ICCC–RWGS. In conclusion, the utilization of superstructures with superior redox reactivity and structural stability, such as perovskite and spinel, offers valuable insights into the design of DFMs for ICCC.
研究领域:
材料科学
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化学工程
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
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2020
·
IF 7.888
Lei Liu,Xiao-Chao Chen,Shu-Qing Yang,Yin-Qing Yao,Yong Lu,Ye Liu
Formic acid (FA) is one kind of important bulk chemicals, which is recognized as a sustainable and eco-friendly energy carrier to transport H 2 via dehydrogenation or CO via decarbonylation. Expectantly, FA upon decomposition into H 2 and CO could be used as the syngas alternative for hydroformylation. In this paper, the behaviors of FA to release H 2 as well as CO following the distinct pathways were carefully investigated for the first time, and then established a new hydroformylation protocol free of syngas. It was found that the atmospheric hydroformylation of olefins with formic acid (FA) as syngas alternative was smoothly fulfilled over Xantphos ( L1 ) modified Rh-catalyst under mild conditions (80 °C, Rh concentration 1 mol %, 14 h), resulting in >90% conversion of the olefins along with the high selectivity to the target aldehydes (>93%). By using FA as syngas source, the side-reaction of olefin-hydrogenation was greatly depressed. The in situ FT-IR and the high-pressure 1 H NMR spectroscopic analyses were applied to reveal how FA behaves dually as CO surrogate and hydrogen source over L1 -Rh(acac)(CO) 2 catalytic system, based on which the deeply insight into the catalytic mechanism of hydroformylation of olefins with FA as syngas alternative was offered.
研究领域:
催化化学
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绿色化学
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能源化学
✓ 已验证
DOI
高影响因子
CHEMICAL RESEARCH IN CHINESE UNIVERSITIES
·
2023
·Vol. 39
·期 6
·1064-1069
·
IF 3.1
He Huan,Zou Zhengxi,Hua Weiming,Yue Yinghong,Gao Zi
A series of ZnO-modified cobaltous ion exchanged ZSM-5 catalysts is prepared using incipient wetness impregnation and characterized by X-ray diffraction (XRD), N 2 adsorption, transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (DR UV-Vis), X-ray photoelectron spectroscopy (XPS), pyridine-adsorbed Fourier transform infrared (Py-IR) and Raman. Their catalytic performance towards CO 2 -assisted dehydrogenation of ethane to ethylene has been evaluated. The addition of ZnO onto CoZSM-5 obviously improved the yield of ethylene as well as the conversion of CO 2 . The promoting effect is attributed to the good activity of ZnO for the reverse water gas shift (RWGS) reaction, which enhances the coupling between RWGS and ethane dehydrogenation.
研究领域:
催化化学
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化学反应工程
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材料科学
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环境化学
✓ 已验证
DOI
高影响因子
EES Catalysis
·
2023
·Vol. 2
·期 1
·365-378
·
IF 0
Yaqi Hu,Zhong Liang,Yabin Zhang,Yaping Du,Hongbo Zhang
Hydrogen production with high efficiency and low CO selectivity in methanol steam reforming (MSR) is of pivotal importance. However, there is limited understanding of the active sites and reaction mechanisms during catalysis. In this study, we maximized the interfacial site, known as the active component in MSR, of Ni–CeOx by atomically dispersed Ni and Ce over the carbon–nitrogen support to generate the Ni and Ce dual-atomic catalyst (DAC), which achieved 6.5 μmolH2 gcat.−1 s−1 H2 generation rate and 0.8% CO selectivity at 99.1% methanol conversion at 513 K. The finely dispersed Ni and Ce structure was confirmed by systematic characterization of AC HAADF-STEM and EXAFS. Electron transfer from Ce to Ni was confirmed simultaneously by quasi-in situ XPS analysis. Moreover, the reaction mechanism of methanol steam reforming was clarified by combining kinetic studies with isotope-tracing/exchange analysis (i.e., KIEs and steady-state isotopic transient kinetic analysis (SSITKA)), which suggests that the steam reforming consists of two tandem reaction processes: methanol decomposition (MD) and water–gas shift (WGS) reaction, with methanol and water activation at independent active sites (e.g., Ni and oxygen vacancy over CeOx), and that hydrogen generation was primarily determined by both C–H bond rupture and OL–H (OL represents the lattice oxygen) cleavage within methoxy and hydroxyl groups, respectively, with the catalytic surface mainly covered by CO and methoxy groups. A shift of WGS involvement in hydrogen generation from negligibly influenced to significantly promoted was selectively observed once modifying the reaction from differential conditions to a high methanol conversion regime, and two quantification methods have been established by comparing the molecule ratio between CO and CO2 or H2.
研究领域:
催化化学
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能源科学
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材料科学
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表面化学
✓ 已验证
DOI
APPLIED CATALYSIS A-GENERAL
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2019
·
IF 4.63
Yuhai Sun,Jingjing Li,Peirong Chen,Bangfen Wang,Junliang Wu,Mingli Fu,Limin Chen,Daiqi Ye
Palladium-loaded ZnO (Pd/ZnO) catalyst was synthesized by co-precipitation method and evaluated for plasma-catalytic reverse water-gas shift (RWGS) reaction. A CO 2 conversion of 32.5 % was achieved on “Pd/ZnO + Plasma”, and was around two times higher than that of “ZnO + Plasma” (17.3 %). Catalyst characterization by X-ray diffraction, high-resolution transmission electron microscopy, temperature-programmed reduction and quasi in situ X-ray photoelectron spectroscopy revealed the possible formation of ZnO x @PdZn (ZnO x decorated PdZn alloy) at the interface of Pd active phase and ZnO support. The role of ZnO x @PdZn in plasma-catalytic CO 2 conversion was systematically investigated by plasma-excited CO 2 temperature-programmed desorption and in situ Fourier transform infrared spectroscopy. It was found that ZnO x @PdZn at Pd-ZnO interface improved significantly plasma-catalytic CO 2 conversion by promoting the production of bidentate carbonate and bidentate formate species. In situ Raman spectroscopy studies proved that the ZnO x @PdZn remained largely intact during the RWGS process. Our in situ spectroscopic findings thus unveil that the ZnO x @PdZn at Pd-ZnO interface favors the activation of CO 2 , and, consequently, leads to a higher plasma-catalytic performance for CO 2 conversion.
研究领域:
化学工程
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2020
·
IF 4.551
Yapeng Xiang,Jie He,Na Sun,Yuteng Fan,Liming Yang,Caihong Fang,Long Kuai
The atomically dispersed catalysts have aroused great attention in the recent decade. However, the preparation of atomically dispersed Au catalysts presents more challenge than other atomically dispersed catalysts such as Pt, Pd, etc. From the aspect of support, this work contributes a novel hollow mesoporous CeO 2 microspheres (CeO 2 -hm) for efficient dispersion of single Au atoms (Au 1 ). Contributed by the high specific surface area and mesoporous structure, CeO 2 -hm possesses much higher capacity for undertaking Au 1 , than commercial CeO 2 particles (CeO 2 -c). Typically, with Au loading of 0.2 at%, CeO 2 -hm supported Au (Au 1 /CeO 2 -hm) presents atomic dispersion while CeO 2 -c supported Au (Au/CeO 2 -c) contains large amount of Au nanoparticles . Confirmed by catalyzing the water-gas shift (WGS) reaction, the obtained Au 1 /CeO 2 catalysts exhibit notably higher performance than the Au-based catalysts supported by CeO 2 -c and CeO 2 synthesized through co-precipitation and sol-gel strategies. For example, 0.2 at% Au 1 /CeO 2 -hm exhibits 9.1 times reactivity of equal Au loaded Au/CeO 2 -c catalyst. Besides, the CeO 2 -hm supported single-atom Au catalyst presents good tolerance under long-time WGS running.
研究领域:
催化化学
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纳米材料科学
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能源化学
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表面科学
·
无机功能材料
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）