Chemistry-An Asian Journal
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2022
·Vol. 17
·期 24
·e202200993
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IF 4.839
Zhijie Zhu,Xu Hu,Xingda An,Mengqi Xiao,Liang Zhang,Chaoran Li,Le He
Graphical The influence of the composition of bimetallic nanocrystals on their performance of photothermal catalytic CO 2 hydrogenation was investigated. Pd and Ni play different roles in the photothermal catalytic processes in the bimetallic system, which leads to a functional tradeoff over the stoichiometric ratio. Bimetallic nanomaterials exhibit excellent catalytic performance in photothermal CO 2 hydrogenation due to the synergistic effect between the two metal components. However, the component-performance relationship remains unclear, which hinders the design of efficient bimetallic catalysts and the investigation of catalytic reaction mechanism. Here we illustrate the influence of the composition of binary alloy on their performance of photothermal catalytic CO 2 hydrogenation by using monodispersed Pd−Ni nanocrystal as an example. Our study reveals that Ni and Pd play a significantly different role in the catalytic processes. Higher Ni component in the catalysts could lead to stronger light absorption, higher activity, and lower CO selectivity. The optimized Pd 4 Ni 1 −SiO 2 catalyst exhibited a near-unity and stable CO production rate of 230 mmol ⋅ g −1 ⋅ h −1 under 25-sun illumination. This study paves the way for the usage of bimetal in photothermal CO 2 catalysis towards more efficient solar-to-chemical energy conversions, and sheds light on some general design principles of bimetallic catalysts to balance the intrinsic properties of individual components.
研究领域:
材料科学
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催化化学
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能源转换
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DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Guiming Xie,Xingyang Bai,Yanrui Niu,Runduo Zhang,Jian Liu,Qingyuan Yang,Zhou-Jun Wang
Making use of novel materials to develop efficient catalysts is one of the research hotspots for CO2 hydrogenation to methanol. Herein, UiO-66, a typical Zr-MOF, was modified by ethylene diamine tetraacetic acid (EDTA) to serve as a substrate for the synthesis of AuCu bimetallic catalysts. The resultant AuCu@UiO-66-EDTA catalyst exhibited a superior methanol production rate, which delivered a high space-time yield of methanol (3.34 gMeOH gmetal–1 h–1) at 250 °C and 3.0 MPa. The EDTA modification was found to effectively confine AuCu nanoparticles inside the framework of MOFs, which significantly reduced the metal particle size and enriched the oxygen vacancy concentration. As a consequence, more active sites were generated for methanol synthesis. Moreover, the AuCu@UiO-66-EDTA catalyst yielded more favorable reaction intermediates that could be converted to methanol at a faster rate. This work develops unique MOFs-encapsulated bimetallic catalysts and illuminates the positive effect of confinement.
研究领域:
材料科学
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催化化学
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DOI
PubMed
高影响因子
APPLIED SURFACE SCIENCE
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2024
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IF 6.3
Min Chen,Longgang Liu,Xueyan Chen,Xiaoxiao Qin,Kunlin Li,Jianghao Zhang,Xiaolei Bao,Lingjuan Ma,Changbin Zhang
The influence of metal particle size over heterogeneous catalysts on the catalytic performance has always been an interesting subject due to its significance from both fundamental and practical perspectives. In this work, we regulated the synthesis of TiO 2 by the hydrolysis of different titanium precursors, and as-prepared TiO 2 supports were employed to load Ru with impregnation method. Interestingly, we synthesized three Ru-TiO 2 catalysts with different Ru particle sizes of 1.1, 2.9 and 5.2 nm. The Ru-TiO 2 catalysts were next tested for CO 2 hydrogenation reaction, the results show that the medium Ru particles on TiO 2 exhibited the best CO 2 methanation activity. Based on the characterizations, we observed that the medium Ru particles exhibited the best redox properties compared with small and large Ru particles, which was beneficial to the H 2 dissociation; in addition, the medium Ru particles exhibited a moderate ability to activate CO 2 , resulting in the most favorable formation and decomposition of bidentate bicarbonate. Consequently, the Ru-TiO 2 catalyst with medium Ru particles showed the highest activity for CO 2 methanation. This study provides a new method to prepare Ru-TiO 2 catalysts with different Ru sizes and also presents an understanding of Ru particle size effects on CO 2 hydrogenation.
研究领域:
催化化学
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材料科学
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高影响因子
Science China-Chemistry
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2019
·Vol. 62
·期 12
·1710-1719
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IF 6.085
Wang Guishuo,Luo Ran,Yang Chengsheng,Song Jimin,Xiong Chuanye,Tian Hao,Zhao Zhi-Jian,Mu Rentao,Gong Jinlong
Metal oxide-promoted Rh-based catalysts have been widely used for CO 2 hydrogenation, especially for the ethanol synthesis. However, this reaction usually suffers low CO 2 conversion and alcohols selectivity due to the formation of byproducts methane and CO. This paper describes an efficient vanadium oxide promoted Rh-based catalysts confined in mesopore MCM-41. The Rh-0.3VO x /MCM-41 catalyst shows superior conversion (~12%) and ethanol selectivity (~24%) for CO 2 hydrogenation. The promoting effect can be attributed to the synergism of high Rh dispersion by the confinement effect of MCM-41 and the formation of VO x -Rh interface sites. Experimental and theoretical results indicate the formation of til-CO at VO x -Rh interface sites is easily dissociated into *CH x , and then *CH x can be inserted by CO to form CH 3 CO*, followed by CH 3 CO* hydrogenation to ethanol.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
ChemCatChem
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2025
·Vol. 17
·期 6
·e202401780
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IF 3.9
Jingru Li,Siyuan Hu,Longmei Shang,Guowu Zhan
Graphical This study investigates N -doped Co 3 O 4 /Pt catalysts synthesized using a Pt-decorated ZIF-67 sacrificial template, followed by a water-soaking treatment to enhance surface hydroxyl (-OH) group content. The interfacial N -stabilized Co 3+ -OH-Pt active sites in N -Co 3 O 4 /Pt improved synergy between cobalt and platinum, enhancing agglomeration resistance and enhancing catalytic performance. CO 2 hydrogenation is a promising method for converting CO 2 into valuable products. Cobalt-based catalysts are favored for their low cost and high activity, but they face challenges from sintering-induced deactivation. This study investigates N -doped Co 3 O 4 /Pt catalysts synthesized using a Pt-decorated ZIF-67 sacrificial template, followed by a water-soaking treatment to enhance surface hydroxyl (─OH) group content. The as-designed N -Co 3 O 4 /Pt catalyst achieved a CO 2 conversion of 64% and CH 4 selectivity of 98% at 340 °C under ambient pressure. It was demonstrated that the interfacial N -stabilized Co 3+ -OH-Pt active sites in N -Co 3 O 4 /Pt improved synergy between cobalt and platinum, enhancing agglomeration resistance and enhancing catalytic performance. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) demonstrated that CO 2 is converted to methane mainly through a formic acid pathway, with no CO detected. This work underscores the critical role of surface hydroxyl groups in promoting CO 2 adsorption and activation, guiding the CO 2 methanation reaction toward efficient methane production.
研究领域:
催化化学
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材料科学
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环境科学
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DOI
高影响因子
Nanoscale
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2025
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IF 5.1
Yubin Zheng,Zhe Lu,Zhisheng Shi,Lu Wang,Shuyuan Yang,Runzhi Cao,Gao Wa,Xin Zhou,Yong Yang,Chong Sheng,Yong Zhou,Zhigang Zou
A highly dispersed NiCo alloy catalyst derived from NiCo bimetallic–organic framework nanosheets was synthesized for efficient photothermal catalysis for CO2 hydrogenation to methane. The NiCo bimetal catalyst achieves a CH4 production rate of 55.60 mmol g−1 h−1 with only a 18.82% decline in performance after 86 hours under atmospheric pressure at selected 290 °C and continuous flow reaction. In situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) reveals the synergistic and complementary roles of light and heat in photothermal catalysis. The thermochemical process drives the reverse water–gas shift reaction to form a *CO intermediate, a key intermediate for the formation of CH4, and light irradiation-generating strong near field from the surface plasma resonance of NiCo bimetals promotes the subsequent *CO hydrogenation step to form *CHO, the rate-determining step for the hydrogenation of CO2 into CH4. Meanwhile, density functional theory (DFT) calculations suggest that the NiCo bimetallic catalyst can also lower the energy barrier of *CO hydrogenation, facilitating the formation of *CHO.
研究领域:
催化化学
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材料科学
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环境科学
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DOI
PubMed
高影响因子
Molecular Catalysis
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2021
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IF 5.062
Jing Zhao,Hucheng Zhang,Haiyan Wang,Jianji Wang
A highly attractive aim is to turn CO 2 into useful chemicals selectively and efficiently, but it still retains great challenging to understand the relations between catalytic performances and interface properties. Here, we report an alternative solution to relate the catalytic activity with the strengths of Lewis acids and bases on the Pd-CoO x interfaces. CoO∙TiO 2 /TiO 2 and CoO x /TiO 2 possess the wide spectrum of Lewis acid/base centres, and give the low selectivity and conversion. The introduction of Pd can focus them on the intrinsic centres, and makes Pd-CoO∙TiO 2 /TiO 2 and Pd-CoO x /TiO 2 represent the ideal catalysis. With temperature-programmed desorptions of CO 2 , CO and NH 3 , it is evidenced that the catalytic hydrogenations of CO 2 to CO, CH 4 and CH 3 OH depend on the cooperation of the Lewis acidic/alkaline centres on the interfaces. The studies provide guidelines for rational design and synthesis of heterogeneous catalysts including but not limited to CO 2 hydrogenation.
研究领域:
化学工程
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催化科学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2023
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IF 7.3
Qiangqiang Wu,Hanke Li,Guangxing Yang,Yonghai Cao,Hongjuan Wang,Feng Peng,Hao Yu
A variety of adsorbed intermediates have been extensively assigned during CO 2 hydrogenation on Pt/γ-Al 2 O 3 . However, the surface sites where the surface species reside have not been well resolved, which are extremely important to depict the reaction pathways of CO 2 hydrogenation. In the current work, surface species adsorbed on three regions were distinguished by in situ diffuse-reflectance infrared Fourier transform spectroscopy, i.e., contiguous Pt region of Pt nanoparticle, interfacial Pt int -O-Al int region between Pt nanoparticle and γ-Al 2 O 3 , and surface region of γ-Al 2 O 3 away from Pt nanoparticle. The dynamics of adsorbed H species, carbonyl species, bicarbonates, formate species, and adsorbed CO 2 , were identified at different sites, proving that the reaction occurs at the Pt/γ-Al 2 O 3 interface. We found that only the C-containing species at the Pt perimeter are directly active intermediates for the reaction. Such spatial analysis bridges the gap between the hydrogen activation and CO 2 activation, providing a deep understanding of CO 2 hydrogenation. In addition, the interface structure with oxygen vacancy is important for CO 2 activation, driving the reaction through carboxylate (*HOCO) pathway to form CO at the interface rather than formate (*HCOO) pathway and then be hydrogenated at the Pt surface.
研究领域:
催化化学
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材料科学
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高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Yanqiu Wang,Ying Zhou,Xinxin Zhang,Mingrui Wang,Tangkang Liu,Jinxing Wei,Guanghui Zhang,Xinlin Hong,Guoliang Liu
Direct CO 2 hydrogenation to higher alcohols (HA) is a promising route for high-value utilization of waste CO 2 , but developing active and stable catalysts remains a grand challenge. For this reaction, constructing multifunctional interfaces as active sites is required to fulfill controllable C-C coupling of alkyl and CO*/CH x O* species. Herein, we report a PdFe catalyst with abundant PdFe alloy-Fe 5 C 2 interfaces via a PdFe alloy induced FeO x carbidization process, which can achieve HA yield of 86.5 mg g cat −1 h −1 with 26.5% selectivity at 300 ºC, 5 MPa, and 6000 mL g cat −1 h −1 . The accelerated deactivation test unveils the PdFe catalyst exhibits better durability than the widely studied CuFe based catalysts against harsh conditions. Multiple in-situ characterization results unveil a synergetic mechanism for HA synthesis at the PdFe alloy-Fe 5 C 2 interfaces, where PdFe alloy is responsible for CO formation and non-dissociative activation, while Fe 5 C 2 phase promotes CO dissociation and chain propagation.
研究领域:
化学工程
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催化科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS LETTERS
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2024
·
IF 2.3
Liu Hang,Liu Sixu,Liang Yaozhen,Sun Yifei,Xiong Haifeng
Palladium (Pd)-based catalysts are widely used for CO 2 hydrogenation reactions due to the capability to activate H 2 , which enhances the overall CO 2 conversion. However, most of the current Pd catalysts reported show high CO 2 conversion only at higher temperature, and the exploration of efficient catalyst enabling low temperature conversion (180–300 °C) is of importance. In this study, a series of Pd-B/ZnAl 2 O 4 catalysts were synthesized via in-situ doping, resulting in the Pd crystal transformation induced from crystal to amorphous. The catalytic hydrogenation activity of the amorphous Pd-B catalyst reaches its zenith at a Pd-B mole ratio of 1:2, accompanied by the superior catalysis stability in CO 2 hydrogenation. Various characterization techniques, including XRD, CO-DRIFTS, H 2 -TPR, XPS and TEM, were used to investigate the properties of the Pd-B/ZnAl 2 O 4 catalyst. The results showed that the Pd-B/ZnAl 2 O 4 catalyst exhibited higher dispersion and better CO 2 conversion efficiency compared to unmodified Pd catalyst. Additionally, the methanol space–time yields are nearly doubled when the B decoration is employed. At 280 °C, CO 2 conversion was improved and methanol selectivity remained at ~ 65%. This study provides valuable insights into the design and optimization of Pd-B based catalysts for CO 2 hydrogenation at low temperatures. Graphical Abstract
研究领域:
催化化学
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能源化学
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材料科学
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DOI
高影响因子
CATALYSIS TODAY
·
2019
·
IF 4.888
Lei Zhang,Hao Wang,Chengguang Yang,Xiaopeng Li,Jian Sun,Hui Wang,Peng Gao,Yuhan Sun
The present work reports on the promoting effects of rare earth elements (La, Ce and Y) to FeK/Al 2 O 3 catalysts on liquid hydrocarbons from CO 2 hydrogenation. The addition of La, Ce and Y can both improve the selectivity of C 5+ hydrocarbons and reduce the selectivity of CH 4 . The C 5+ selectivity can enhance to about 60 % with CH 4 selectivity of around 11 % at CO 2 conversions above 20 %. N 2 adsorption–desorption, in situ XRD, H 2 –TPR, CO 2 /H 2 –TPD, HRTEM and XPS are used to characterize the FeK/Al 2 O 3 and FeK/M-Al 2 O 3 (M = La, Ce, Y) catalysts. The results show that the introduction of rare earth elements into the FeK/Al 2 O 3 catalyst obviously reduces the adsorption of H 2 , which suppresses the CH 4 formation. On the other hand, rare earth elements also promote the adsorbed CO 2 species, which leads to the enhanced liquid hydrocarbons selectivity. Finally, the tailored CO 2 /H 2 ratio of CO 2 and H 2 adsorption on the catalyst surface can influence the catalyst activity and the product selectivity evidently.
研究领域:
催化化学
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材料科学
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环境科学
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DOI
高影响因子
Catalysis Science & Technology
·
2019
·Vol. 9
·期 10
·2673-2681
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IF 5.726
Bing Hu,Yazhi Yin,Zixin Zhong,Dengdeng Wu,Guoliang Liu,Xinlin Hong
Maximizing the Cu–ZnO interface is regarded as the best strategy to promote methanol synthesis activity over CuZn catalysts. Reducing the ZnO particle size can enhance the Cu–ZnO interaction, but its synthesis with a sub-5 nm size still remains a challenge. Moreover, the fabrication of an active powder catalyst with an inverse ZnO/Cu configuration is still very rare. In this work, we report a facile synthesis of inverse ZnO/Cu catalysts by direct calcination of Cu@ZIF-8 (zeolitic imidazolate framework-8). The particle size of ZnO and Cu can be tuned by changing the Cu loading as well as the calcination temperature. Importantly, inverse ZnO/Cu catalysts with sub-5 nm ZnO were obtained under gentle calcination at 623 K. In the CO2 hydrogenation reaction, the highest methanol synthesis activity reached 933 g kgcat−1 h−1 at 533 K and 4.5 MPa, with a high turnover frequency (TOF) of 0.013 s−1, over an optimized C2Z-623 catalyst, which exceeds the commercial CuZnAl catalyst (HiFuel R120, Johnson Matthey) and has ranked the top reported value over advanced CuZn catalysts under comparable conditions. Such excellent activity is attributed to the inverse structure of Cu particles covered by sub-5 nm ZnO, which promotes the intimate Cu–ZnO interface with enhanced SMSI. Moreover, we find that the methanol turnover frequency (TOF) monotonically increases with decreasing the particle size of ZnO as well as Cu. It is proposed that reducing the ZnO size favors the spillover of reducible ZnOx species onto the Cu surface while lowering the Cu size is responsible for the enhanced amount of exposed Cu steps for accommodating Zn species, both of which could facilitate the formation of Zn covered Cu steps as active sites for methanol synthesis.
研究领域:
化学工程
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催化材料科学
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DOI
高影响因子
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