APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
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IF 24.319
Guiming Xie,Rongrong Jin,Pengju Ren,Yunming Fang,Runduo Zhang,Zhou-jun Wang
Boosted CO 2 hydrogenation to methanol was achieved by introducing appropriate amount of Au into conventional Cu-based catalysts. The Au x Cu/ZnO bimetallic catalysts with various Au/Cu molar ratio (x = 0.001, 0.005, 0.02 and 0.05) were prepared by the co-precipitation method, among which the Au 0.005 Cu/ZnO catalyst exhibited the highest methanol production rate. The formation of Au-Cu alloy was identified on the Au x Cu/ZnO bimetallic catalysts. Experimental characterizations and density functional theory (DFT) calculations suggested metal-oxide interfaces with oxygen vacancies as intrinsic active sties for both un-promoted and Au-promoted Cu/ZnO catalysts. The promotion effect of Au in bimetallic catalysts was correlated with the increase of active sites, facilitation of CO 2 activation and modification of intermediate adsorption. The present work for the first time develops a promising Au 0.005 Cu/ZnO bimetallic catalyst with trace amount of Au (only 0.4 wt%) and provides insight into the reaction mechanism over Au-promoted Cu/ZnO catalysts for methanol synthesis via CO 2 hydrogenation.
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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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Xiuqin Ci,Dong Zhai,Rui Tu,Xiaoju Li,Shuchao Jiang,Xinbo Wang,Weiqiao Deng,Guoqing Ren
CO 2 hydrogenation into formic acid is of great significance to mitigate CO 2 emission. However, conventional routes typically require the addition of unrecyclable bases to shift the reaction equilibrium by the formation of formate, which leads to complex subsequent separation and difficulty in continuous production of pure formic acid solution. Here we report a secondary amine-modified PdMn nanocatalyst for the continuous production of pure formic acid solution in fixed-bed reactors via CO 2 hydrogenation. By optimizing fine structure of PdMn nano-alloy, the optimal TOF of up to 26.5 h −1 is obtained under mild reaction conditions (25 ℃, 3.0 MPa). This is one of the highest levels reported for a heterogeneous catalyst without alkali additives under similar conditions. The characterization shows that the two-component alloying effect of PdMn and the synergistic effect between PdMn NPs and secondary amine group (NH) are the key to obtaining superior reactivity. These findings in this work may pave an avenue for conversion of CO 2 in a more environmentally friendly way.
研究领域:
化学工程
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环境科学
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催化材料
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产品关联
DOI
高影响因子
JACS Au
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2025
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IF 8.7
Xuan Bie,Yukun Pan,Xiaowei Wang,Shiyu Zhang,Jiahui Hu,Xiaoxiao Yang,Qinghai Li,Yanguo Zhang,Robert E. Przekop,Yayun Zhang,Hui Zhou
Gas sources rich in CO2 derived from biomass/waste gasification, anaerobic digestion, or industrial carbon capture often contain impurities such as H2S, H2O, and NH3, which can significantly hinder catalyst performance. Here, we show the role of NH3 on the reverse water–gas shift (RWGS) reaction over a commercial Cu/ZnO/Al2O3 catalyst, examining its effects on both the catalytic activity and the catalyst structure. We found that NH3 reversibly decreases CO2 conversion immediately by suppressing carbonate hydrogenation and CO desorption. This effect intensifies with an increase in NH3 concentration but decreases at higher temperatures. However, prolonged exposure (over 100 h) to RWGS conditions in the presence of 1.4% NH3 leads to near-total and irreversible deactivation of the Cu/ZnO/Al2O3 catalyst. Under NH3 exposure, the catalyst loses Cu+ sites on the surface, causing a spatial separation of Cu and ZnO. Finally, to address this challenge, we propose a novel strategy to mitigate NH3 inhibition by decomposing NH3 into N2 and H2.
研究领域:
化学工程
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催化科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Linkai Wang,Yu Han,Jian Wei,Qingjie Ge,Shijian Lu,Yanpeng Mao,Jian Sun
Hydrogenation of CO 2 into light olefins is an important route to carbon neutrality . Most of traditional researches focus on the catalyst component, structure, and promoter to enhance the selectivity of light olefins while ignoring the diffusion of products. Here, we report a NaFeZr-MOR composite catalyst for light olefin synthesis in CO 2 hydrogenation via pore confinement. The selectivity in hydrocarbons and STY (Space-time yields) of C 2–4 = is gradually increasing maximum up to 51.3% and 12.2 (mmol·g cat −1 . h −1 ), which lie in a high level among reported Fe-based catalysts. Further characterization revealed that the essence of selectivity change period is the accumulation and evolution of carbonaceous species, which causes the change of product diffusion behavior. It suppresses the escape of heavy hydrocarbons from MOR pores, leading to an increased light olefin, especially ethylene, which is called “dynamic confinement”. These findings provide a new insight for controlling low-carbon product selectivity in 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
Catalysts
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2023
·Vol. 13
·期 5
·800
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IF 3.9
Zhong Xie,Jinpei Hei,Lei Cheng,Jing Li,Xiaojie Yin,Sugang Meng
CO2hydrogenation to methanol was conducted using a set of activated carbon-supported Cu/ZnO/Al2O3catalysts (CCZA) prepared by an incipient wetness impregnation approach. The effect of the Cu/Al ratio on the physicochemical properties of the catalysts, as well as their catalytic performance, were investigated. As Cu/Al ratio increased, the metallic Cu surface area displayed a reducing trend from 6.88 to 4.18 m2∙gcat−1, while the CO2adsorption capacity exhibited an increasing trend. Meanwhile, aluminum content will have an important effect on the catalysts’ reducibility and, thus, on their catalytic performance. The CCZA-2.7-de catalyst demonstrated the highest selectivity to methanol at 83.75% due to the excellent distribution and synergistic effect of copper and zinc. Although the CO2conversion of CCZA-2.2-de and CCZA-3.5-de exceeded 10%, the CH3OH selectivity was less than 60%, which may be attributed to the larger particle sizes of ZnO and poor interactions in Cu–Zn. The present study offers a novel approach to increase the number of active sites, optimize the activated carbon-aided Cu/ZnO/Al2O3catalyst’s composition, and finally elucidate the mechanism for CO2hydrogenation to methanol.Keywords:CO2hydrogenation;CuO/ZnO/Al2O3catalyst;methanol synthesis;carbon-supported catalyst;thermocatalysis
研究领域:
催化
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化学工程
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环境科学
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DOI
高影响因子
FUEL
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2022
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IF 8.035
Yihua Yue,Zhongliang Huang,Dongren Cai,Shafqat Ullah,Abdul-Rauf Ibrahim,Xin Yang,Jiale Huang,Guowu Zhan
Controlled fabrication of spatial positions of different active sites on catalyst structures is critical to exploring the reaction mechanisms for CO 2 hydrogenation. Herein, two isomorphous zeolitic imidazolate frameworks (ZIF-67 and ZIF-8) were used as sacrificial templates to synthesize multi-layered Co 3 O 4 /ZnO catalysts with tunable core-shell structures and well-controlled spatial positions. The multi-layered catalysts were then evaluated for the catalytic performance for CO 2 hydrogenation. A series of characterization techniques were applied to investigate the morphology and structure of the Co 3 O 4 /ZnO composites with different spatial locations. Due to the unique multi-layered structure, the distinct interfacial structures, and the synergistic effects, the resultant core-shell structured Co 3 O 4 /ZnO nanocatalysts exhibited significantly enhanced activity as compared to their monometallic counterparts (pure Co 3 O 4 and ZnO). In addition, the ZnO@Co 3 O 4 with Co 3 O 4 as shell showed significantly higher CO 2 conversion (25%) than that of Co 3 O 4 @ZnO with ZnO as shell (0.82%). Furthermore, in-situ Diffuse Reflection Fourier Transform Infrared Spectroscopy (DRIFTS) analysis suggested that formate (HCOO*) and methoxy (CH 3 O*) species were the crucial intermediates in the CO 2 hydrogenation over the Co 3 O 4 /ZnO composite nanocatalysts. However, pure ZnO could not activate the CO 2 ; consequently, the use of the Co 3 O 4 /ZnO nanocatalysts derived from multiple-layered ZIFs structures provides new insights into improving the catalytic efficiency of CO 2 hydrogenation.
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
AICHE JOURNAL
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2024
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IF 3.5
Jinyan Zhang,Yan Shao,Feng Zeng,Huanhao Chen
Secondary-metals promotion is key to tune the CO 2 hydrogenation performance of Rh-based catalyst. We describe the addition of Cu or Co in TiO 2 nanorods supported Rh catalyst (viz., RhM x /TiO 2 ), showing significant impact on the CO 2 hydrogenation activity and productivity. Cu addition can promote the partial hydrogenation to alcohols (methanol and ethanol), whereas Co led to the deep hydrogenation to alkanes (CH 4 , C 2 H 6 ). Comparative time-resolved in situ DRIFTS studies with H 2 /D 2 isotopic exchange further reveal that both surface adsorbed CO* and formates could be the key reaction intermediates during the CO 2 hydrogenation over RhM x /TiO 2 (especially the RhCu 2.5 /TiO 2 ), in which the interaction strength of CO* regulated by secondary-metals addition was key to tune the reaction pathways and productivity. The findings suggested that rational design of active metal sites, for example the synergy between Rh and secondary-metals, is highly needed to promote the CO insertion and C C coupling to produce ethanol.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2021
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IF 7.132
Miaomiao Song,Zhongliang Huang,Bin Chen,Sihan Liu,Shafqat Ullah,Dongren Cai,Guowu Zhan
Catalyst design is one of the most critical factors in selectively converting CO 2 and renewable H 2 to value-added chemicals. In this work, Pt nanoparticles with an average size of 2.9 nm were uniformly loaded on hollow mesoporous nickel phyllosilicate which then underwent various reduction treatments to partial extraction of Ni atoms and formation of Ni-Pt bimetallic catalysts for the selective CO 2 hydrogenation in a fixed bed reactor. Experimental results reveal that Pt nanoparticles supported on SiO 2 are highly selective to CO via reversed water gas shift (RWGS) reaction with 100% CO selectivity, while Pt nanoparticles supported on nickel phyllosilicate show high selectivity for CH 4 , particularly, under high reduction temperature. By simply changing the reduction temperature or reaction pressure, the production selectivity can be facilely tuned, and the maximum CH 4 selectivity achieved in the bimetallic Pt/Ni@phyllosilicate catalyst is 100%. The metallic Ni 0 reduced from nickel phyllosilicate owns a high concentration of Lewis basic sites, which could enhance the adsorption strength of CO 2 but prevent the dissociated adsorption. The diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) in different transient states were applied to study the mechanistic insights into how Ni-Pt dual sites tune the product selectivity. The results suggest that CO* over Pt site is the key species for CO 2 conversion to CO, whereas the produced CO* could be further hydrogenated to CH x O* intermediate over Ni site, leading to the formation of CH 4 . The present work offers a new method to prepare Ni-Pt bimetallic catalysts with excellent CO 2 hydrogenation performance towards CH 4 .
研究领域:
催化化学
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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
CATALYSIS TODAY
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2025
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IF 5.3
Biao Gao,Wenbo Gao,Longtai Li,Tatsumi Ishihara,Limin Guo
The In 2 O 3 -ZrO 2 solid solution catalyst has emerged as a versatile catalytic support for CO 2 hydrogenation to methanol, enabling noble metal-based systems (e.g., Pt, Ir) to achieve improved methanol selectivity. Building on this foundation, we introduce cobalt into the In 2 O 3 -ZrO 2 matrix, creating a novel Co/In 2 O 3 -ZrO 2 composite catalyst that synergistically integrates transition metal functionality with oxide engineering. The optimized catalyst achieves a methanol space-time yield of 0.80 g MeOH ·gcat −1 ·h −1 at a 5.0 MPa, H 2 /CO 2 = 3:1, 320 °C, GHSV = 48,000 cm 3 · g cat − 1 · h −1 , surpassing reported In 2 O 3 -ZrO 2 and Co/In 2 O 3 benchmarks. Mechanistic studies reveal that methanol synthesis follows the formate pathway, where ZrO 2 amplifies oxygen vacancy density to improve CO 2 adsorption and weakens CO adsorption through electronic modulation.
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
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2025
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IF 4.9
Xiaohong Guo,Liqiang Deng,Xiaoyue Wang,Yongjie Zhao,Zhifan Cao,Pengwei Li,Congming Li
A pivotal aspect in advancing ZrZnO x catalysts for CO 2 hydrogenation lies in the modulation of Zr-O-Zn active sites, with ZnO facets emerging as potential modulators of site activity. Whereas the beneficial influence of non-polar ZnO facets on ZrZnO x catalysts has been scarcely documented. Our investigation reveals that ZrZnO x catalysts exposed non-polar ZnO facets (ZrZnO-n) exhibit superior methanol selectivity (74 %) compared to those with randomly exposed ZnO facets (ZrZnO-r, 35 %). Characterization results demonstrate that it is ascribed to the formation of highly active Zr-O-Zn (2−δ)+ sites on ZrZnO-n, which facilitate H 2 adsorption and dissociation. In situ spectroscopic studies and DFT calculations further substantiate this finding, demonstrating enhanced intermediates formation and more efficient hydrogenation processes. This research underscores the significance of ZnO facet engineering in the purposeful creation of efficient ZrZnO x catalysts for CO 2 hydrogenation.
研究领域:
催化化学
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材料科学
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能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
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2024
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IF 11.3
Yanmei Cai,Cunbiao Lin,Xingwen Cha,Yiling Wu,Xiaoping Rao,Kok Bing Tan,Dongren Cai,Gui-Lin Zhuang,Guowu Zhan
The supported Ni/In2O3 catalysts are of great interest in CO2 hydrogenation, but the formation of the In0 or Ni–In alloy phases due to over-reduction would lead to rapid catalyst deactivation. Herein, thin Al2O3 films were deposited on the Ni/In2O3 surface by atomic layer deposition (ALD) as an antireduction agent, which enables the In2O3 catalyst to maintain a significant abundance of active In3+ species even during high-temperature H2 treatment (400 °C, 2 h), thereby effectively resisting the deactivation caused by over-reduction of In2O3. Various characterization methods confirm the antiover-reduction effect of ALD-Al2O3 films, namely, inhibiting the formation of In0 and In3Ni2 alloys during high-temperature H2 treatment and facilitating the reoxidation of low-valence In to form the active In2O3–x phase in the presence of a CO2 atmosphere. As treated with H2 at 400 °C, the 5Al2O3/Ni/In2O3-R400 catalyst exhibited an STYMeOH of 7.39 gMeOH h–1gNi–1 and a methanol selectivity of 64% (reaction conditions: 3 MPa, 300 °C, and 12,000 mL gcat–1h–1). Particularly, the STYMeOH increased by 11.5 times as compared with that of the Ni/In2O3-R400 catalyst without coating the ALD-Al2O3 layer (0.59 gMeOH h–1gNi–1). Density functional theory (DFT) calculations validate the effectiveness of specific charge transfer tendencies in suppressing the over-reduction of high-valence In species. Through the analysis of the crystal orbital Hamilton population (COHP) and projected density of states (PDOS) electronic structures of the adsorbate species, the Al2O3/Ni/In2O3 catalyst is shown to significantly enhance CO2 activation and further catalytic reactions. Accordingly, this study unveils the deactivation mechanism of In2O3-based catalysts due to over-reduction and provides a method to regulate their reduction level by depositing ALD-Al2O3 films on the In2O3-based catalysts.
研究领域:
催化化学
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材料科学
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理论计算化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
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2023
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IF 8.4
Xianqiang Gao,Lulu Cao,Ying Chang,Zhimin Yuan,Shuxin Zhang,Shujun Liu,Mengting Zhang,Hai Fan,Zaiyong Jiang
Recently, the surface frustrated Lewis pairs (SFLP) have attracted more and more attention in the field of CO2 hydrogenation. The main research studies have focused on a single construction of SFLP; however, the exploration of the synergy between SFLP and other excellent techniques has been barely reported. In this work, a common photocatalyst, TiO2, was chosen as the research object and amorphous TiO2–x(OH)y and CuPt alloy were constructed on its surface to investigate the synergy between SFLP and the metal cocatalyst technique. The amorphous TiO2–x(OH)y could form effective SFLP to increase CO2 activation, and the CuPt alloy was beneficial for H2 dissociation to boost the formation of protonated/hydridic H. The synergy resulted in CuPt/TiO2–x(OH)y/TiO2 exhibiting significantly increased activity for the reverse water gas shift (RWGS) reaction compared to those of TiO2–x(OH)y/TiO2, CuPt/TiO2, and pristine TiO2. This work highlights an important research direction for the SFLP application in the field of CO2 hydrogenation.
研究领域:
催化化学
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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
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