JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
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2025
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IF 6
Guo-Cui Mao,Jin-Peng Wang,Hui-Lin Jiang,Bao-Xia Dong,Yun-Lei Teng
We found that the activated LiBH 4 or Ni/LiBH 4 can effectively assist CO 2 hydrogenation into C1 and C2 products at low temperature (100–300 ℃). After CO 2 hydrogenation over the activated LiBH 4 or Ni/LiBH 4 , CH 4 with approximately 100 % selectivity was formed in the gas phase products. CH 3 OH, HCOO − , and high-value CH 3 CH 2 OH were observed in aqueous solution of spent LiBH 4 or Ni/LiBH 4 after CO 2 hydrogenation. CO 2 conversion and CH 4 production are able to be further improved by doping 5–20 wt% Ni into the activated LiBH 4 . The LiBH 4 sample shows a 61.34 % CO 2 conversion at 200 ℃, while the 20 %Ni/LiBH 4 composite displays an 80.14 % CO 2 conversion under the same conditions. The experimental and theoretical results suggest that the synergistic effect from Ni and LiBH 4 results in high CO 2 conversion at low temperature. This new method for CO 2 conversion to C1, C2 products using the activated Ni/LiBH 4 composite may enlighten the materials design for CO 2 utilization.
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
CHEMICAL ENGINEERING RESEARCH & DESIGN
·
2024
·
IF 3.7
Yunfei Zhao,Hang Sheng,Jiashun Xi,Tingting Jiang,Dong Wang,Jian Zhang,Zheng Li,Bing Wang,Xiaohui Xu,Haifeng Zhang,Bo Yuan,Runlong Hao,Yi Zhao,Tianhao Wang
In the reaction system with NaBH 4 as a hydrogen donor, inhibiting the formation of hydrogen is the key to promote the efficient catalytic hydrogenation of CO 2 . In this study, nanoscale zero-valent nickel supported on carbon nanofibers (Ni 0 /CNFs) was fabricated as a catalyst for CO 2 hydrogenation in aqueous NaBH 4 solution. The characteristics of Ni 0 /CNFs were examined. By SEM, it was observed that spherical nickel nanoparticles were distributed homogeneously on the surface of strip-shaped carbon nanofibers. EDS mappings indicated that elements were evenly distributed on the catalyst, which might contribute to the uniform exposure of active sites. Via XRD, it was determined that all the diffraction peaks corresponded to the crystal face of nickel metal and that the absence of diffraction peaks of carbon nanofibers indicated that the crystallinity of the carrier was low. XPS study showed that nickel existed on the catalyst surface in two forms: zero valence metal and oxidation state. The effects of catalyst addition amount, NaBH 4 concentration, NaOH dosage, stirring rate on the yield of formate and hydrogen generation rate (HGR) were investigated. By optimizing the above parameters, the concentration of formate reached 150 mmol/L and the hydrogen production rate was 10.55 mL/min. Compared with the non-catalytic conditions, the concentration of formate increased by 57 % and the HGR decreased by 78 %. Moreover, the relationship between CO 2 hydrogenation and NaBH 4 hydrolysis was clarified. This research could enhance comprehension of CO 2 hydrogenation in aqueous NaBH 4 solution and contribute to the development of CO 2 capture and utilization storage technology. The significance of this study lies in clarifying the connection between CO 2 hydrogenation and borohydride hydrolysis in CO 2 catalytic hydrogenation technology.
研究领域:
化学工程
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环境科学
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材料科学
✓ 已验证
DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY
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2024
·
IF 11.2
Mengyao Xu,Fei Liu,Shike Liu,Jun Ma,Mengqin Yao,Xiaodan Wang,Jianxin Cao
Metal-based catalysts are prevalent in the CO 2 hydrogenation to methanol owing to their remarkable catalytic activity. Herein, Ru/In 2 O 3 catalysts with different morphologies obtained by doping Ru into In 2 O 3 with irregular, rod-like, and flower-like morphologies are used for catalytic CO 2 hydrogenation to methanol. Results indicate that the flower-like Ru/In 2 O 3 (Ru/In 2 O 3 -F) exhibits higher catalytic performance than Ru/In 2 O 3 with other morphologies, achieving a 12.9% CO 2 conversion, 74.02% methanol selectivity, and 671.36 mg MeOH ·h −1 ·g cat −1 methanol spatiotemporal yield. Furthermore, Ru/In 2 O 3 -F maintains its catalytic stability over 200 h at 5 MPa and 290 °C. The promotional effect mainly stems from the fact that electronic structure of Ru can be effectively adjusted by modulating the morphology of In 2 O 3 . The strong interaction between atomically dispersed Ru and In 2 O 3 -F enhances the structural stability of Ru, inhibiting the agglomeration of the catalyst during the reaction process. Furthermore, density-functional theory calculations reveal that highly dispersed Ru atoms not only perform efficient and rapid electronic gain and loss processes, facilitating the catalytic activation of H 2 into H intermediates. It also enables the generated reactive H to rapidly overflow to the surrounding In sites to participate in CO 2 reduction. These findings provide a theoretical basis for the development of high-performance catalysts for CO 2 hydrogenation.
研究领域:
催化
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材料科学
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化学工程
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Yihua Yue,Jian Tian,Jiechao Ma,Shui Yang,Wen Li,Jiale Huang,Qingbiao Li,Guowu Zhan
Herein, Ga-ZnZrO x &ZSM-5 bifunctional catalysts were designed for CO 2 thermal hydrogenation to aromatics, particularly, aiming to enhance the selectivity of high-value BTX ( i.e. , benzene, toluene, and xylene). It was evident that the exterior surface properties and acidity of ZSM-5 can be effectively tailored by in-situ silicon deposition originating from the rice husk template. Catalytic performance assessments demonstrate an optimized catalyst achieving 88.1 % aromatics selectivity (exclusive CO) in a single pass, with a notable 45.2 % BTX selectivity within total aromatics and a low CO selectivity of 23.6 %. This superior performance is attributed to the in-situ silicon deposition on ZSM-5 during one-pot synthesis and the optimized spacing between Ga-ZnZrO x and ZSM-5 facilitated by the rice husk platform. Furthermore, in-situ DRIFTS analysis identifies key reaction intermediates. This study offers an effective strategy for tuning zeolite acidity using rice husks, while modulating metal oxide-zeolite proximity on the bio-SiO 2 platform, thus boosting CO 2 conversion to aromatics.
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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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Science Bulletin
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2025
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IF 21.1
Wanguo Gao,Zhe Lu,Yecheng Leng,Chengyang Wu,Yingfang Yao,Xi Zhu,Junchuan Sun,Xiwen Yu,Cheng Wang,Congping Wu,Wenlei Wu,Bing Wang,Lu Wang,Zhigang Zou
Cu-based catalysts attract considerable attention because of their exceptional CO 2 photo-/electro-/thermo-reduction capacities, where Cu(I) is generally treated as the active species. However, a significant problem hindering the large-scale applications of Cu-based catalysts is the inactivation of Cu(I) via irreversible redox to Cu(II)/Cu(0). This study proposes a Cu(I) valence pinning method based on hydroxyapatite (HAP). Experimental and theoretical studies demonstrate that the phonon resonance among the Cu(I) ions, their adjacent heteroatoms, and the intermediates adsorbed at the Cu(I) sites yields Cu(I) valence electrons in their lowest energy states. Thus, Cu(I) is stabilized, stable, and efficient photothermal CO 2 hydrogenation is promoted. However, because of the change of Cu(I) coordination environment during the CO 2 hydrogenation reaction, Cu(I) ions migrate into the bulk phase, leading to activity attenuation. Nevertheless, Cu(I) ions can be pulled out to the surface of HAP under the oxidative humid air condition, and the catalytic activity can be easily recovered. Thus, we propose a simple cyclic reaction/regeneration process. This enables the Ca 5 (FeCuCe) 5 -HAP catalyst to achieve the CO yield of 402.8 mmol g −1 h −1 and a CO 2 conversion rate of 27.7%, which is close to the thermodynamic equilibrium. This catalyst also displays a selectivity of approximately 100% and cycle stability of 156 h at 500 °C under a pressure of 1 atmospheric. Our study provides a viable method for the scale applications of Cu(I) based catalysts in the “negative carbon” industries.
研究领域:
材料科学
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环境科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Yuntao Qi,Bin Zhang,Dengrong Xue,Hui Zhang,Xiaoning Liu,Zhi Liu,Shichao Zhao,Zhuo Li,Fanchun Meng,Yong Qin
The catalytic conversion of CO2 to CO through hydrogenation has emerged as a promising strategy for CO2 utilization, given that CO serves as a valuable C1 platform compound for synthesizing liquid fuels and chemicals. However, the predominant formation of CH4 via deep hydrogenation over Ru-based catalysts poses challenges in achieving selective CO production. High reaction temperatures often lead to catalyst deactivation and changes in selectivity due to dynamic metal evolution or agglomeration, even with a classic strong metal–support interaction. Herein, we have developed a FeOx/Ru/Rutile multilayer epitaxial structure by depositing a FeOx layer onto the epitaxially grown RuO2 nanolayers on the surface of rutile nanoparticles. This multilayer epitaxial structure transformed into a structure in which Ru nanoparticles were decorated with FeOx layers with ultrastable strong metal-support interaction (SMSI). Subsequently, the FeOx decoration on Ru nanoparticles effectively shifted the dominant product from CH4 to 95% CO during CO2 hydrogenation. Remarkably, this catalyst exhibits exceptional stability and can be operated stably at 550 °C for a long time without apparent deactivation. Compared with the dynamic changes observed in supported Ru nanoparticles, the interaction between Ru and FeOx maintains their electronic states at different reaction temperatures. Furthermore, this Ru–FeOx interaction inhibits H2 activation capability, CO adsorption, and subsequent hydrogenation of CO. The transformation strategy employed here, which utilizes initial multilayer epitaxial structures, can be applied to construct SMSI to enhance metal catalysts’ catalytic performance.
研究领域:
催化
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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
PubMed
高影响因子
Journal of CO2 Utilization
·
2017
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IF 4.292
Chen Zhang,Haiyan Yang,Peng Gao,He Zhu,Liangshu Zhong,Hui Wang,Wei Wei,Yuhan Sun
A series of Cu/ZnO/Al 2 O 3 catalysts with the total weight percentage of Cu and ZnO from 9.94 wt.% to 44.5 wt.% have been prepared by ammonia deposition −precipitation method and tested for methanol synthesis from CO 2 hydrogenation. A Cu/Zn/Al layered double hydroxides (LDHs) precursor can be formed in situ on the surface of microspherical Al 2 O 3 which acts as both support and sole source of Al 3+ cations. With increase of total Cu and ZnO loading, the dispersion of copper and reducibility of CuO decline continuously, while the exposed copper surface area increases gradually. In addition, the formation of LDHs results in a stronger both basicity and acid strength on the catalyst surface. It is found that the CO 2 conversion increases linearly with increase of the Cu and ZnO loading. The methanol selectivity for the catalyst with low total metal loading (9.94 wt.%) is much lower than those for other catalysts, though it increases with increasing loading, which can be mainly assigned to the much smaller Cu particle size (<5 nm) and the higher ratio of isolated CuO phase. Moreover, the Cu/ZnO/Al 2 O 3 catalyst with relatively high total metal loading (44.50 wt.%) still exhibits a considerable stable catalytic performance due to the formation of LDH structure.
研究领域:
催化
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化学工程
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材料科学
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环境化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-9
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IF 14.7
Zhai Jianxin,Xia Zhanghui,Zhou Baowen,Wu Haihong,Xue Teng,Chen Xiao,Jiao Jiapeng,Jia Shuaiqiang,He Mingyuan,Han Buxing
Upcycling of CO 2 into fuels by virtually unlimited solar energy provides an ultimate solution for addressing the substantial challenges of energy crisis and climate change. In this work, we report an efficient nanostructured Ru/MnO x catalyst composed of well-defined Ru/MnO/Mn 3 O 4 for photo-thermal catalytic CO 2 hydrogenation to CH 4 , which is the result of a combination of external heating and irradiation. Remarkably, under relatively mild conditions of 200 °C, a considerable CH 4 production rate of 166.7 mmol g −1 h −1 was achieved with a superior selectivity of 99.5% at CO 2 conversion of 66.8%. The correlative spectroscopic and theoretical investigations suggest that the yield of CH 4 is enhanced by coordinating photon energy with thermal energy to reduce the activation energy of reaction and promote formation of key intermediate COOH* species over the catalyst. This work opens up a new strategy for CO 2 hydrogenation toward CH 4 .
研究领域:
化学
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材料科学
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环境科学
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能源科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of CO2 Utilization
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2022
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IF 8.321
Xiaowei Hu,Maowei Luo,Mooeez ur Rehman,Junhao Sun,Hamzah A.S.M. Yaseen,Faisal Irshad,Yujun Zhao,Shengping Wang,Xinbin Ma
The electron-donating effect of supports on active metals has been reported to be beneficial to improve catalytic activity of heterogenized molecule catalysts for CO 2 hydrogenation to formic acid . However, this effect has not been discussed in depth from the perspective of reaction mechanism, especially for CO 2 activation with the combination of theoretical calculations. Herein, we report a catalyst prepared via anchoring RuCl 3 on a post-synthetic modified (PSM) zeolitic imidazolate framework-8 (ZIF-8) in which linkers 3-methyl-1,2,4-triazole (Mtz) with a surplus of uncoordinated N sites have been incorporated. X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) calculations reveal that uncoordinated N sites in linkers donate additional electron-density to Ru, resulting in the decrease of energy barrier of CO 2 activation. And the RuCl 3 @ZIF-8-Mtz(0.29) catalyst containing the most Mtz ligands displayed the highest catalytic performance for the CO 2 hydrogenation to formic acid as compared to RuCl 3 @ZIF-8-Mtz(0.15) and RuCl 3 @ZIF-8.
研究领域:
催化
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材料科学
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化学工程
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2021
·
IF 4.311
Zhongliang Huang,Yujia Yuan,Miaomiao Song,Zhimian Hao,Jingran Xiao,Dongren Cai,Abdul-Rauf Ibrahim,Guowu Zhan
Herein, we fabricated a series of bimetallic Pt-Ni catalysts supported on mesoporous silica nanorods ( m SNR, specific BET surface area of 1802 m 2 g −1 ) to study the effect of Ni/Pt ratio on the product selectivity in CO 2 hydrogenation. Both monometallic Pt/ m SNR and Ni 50 Pt 50 / m SNR catalysts revealed negligible methane selectivity. However, methane became the major product only when increasing the Ni/Pt ratio up to 9. X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma (ICP) characterizations showed that the Pt/Ni ratio on the catalyst surface was appreciably higher than the bulk composition, suggesting the enrichment of Pt on the surface ( e.g. , Pt/Ni of 61/39 for Ni 50 Pt 50 / m SNR catalyst). The Pt/Ni ratio was crucial in determining the CH 4 /CO selectivity, and the addition of a tiny amount of Pt could improve the catalytic performance and stability of Ni/ m SNR. Among the different catalysts, Ni 98 Pt 2 / m SNR showed the best CO 2 conversion (59%) and CH 4 selectivity (96%) at 400 °C, 0.1 MPa, 9600 mL h −1 g cat −1 , and H 2 /CO 2 of 3. In-situ DRIFTS and temperature-programmed surface experiments suggested that the dissociated adsorption of CO 2 on the Pt site led to CO*, but the strongly adsorbed CO* cannot be further hydrogenated to CH 4 over the Pt site. In contrast, CO* could be further hydrogenated into CH 4 via CH x O* intermediates on adjacent Ni sites.
研究领域:
催化
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材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
JACS Au
·
2022
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IF 0
Yuhai Sun,Junliang Wu,Yaolin Wang,Jingjing Li,Ni Wang,Jonathan Harding,Shengpeng Mo,Limin Chen,Peirong Chen,Mingli Fu,Daiqi Ye,Jun Huang,Xin Tu
Plasma-catalytic CO2 hydrogenation is a complex chemical process combining plasma-assisted gas-phase and surface reactions. Herein, we investigated CO2 hydrogenation over Pd/ZnO and ZnO in a tubular dielectric barrier discharge (DBD) reactor at ambient pressure. Compared to the CO2 hydrogenation using Plasma Only or Plasma + ZnO, placing Pd/ZnO in the DBD almost doubled the conversion of CO2 (36.7%) and CO yield (35.5%). The reaction pathways in the plasma-enhanced catalytic hydrogenation of CO2 were investigated by in situ Fourier transform infrared (FTIR) spectroscopy using a novel integrated in situ DBD/FTIR gas cell reactor, combined with online mass spectrometry (MS) analysis, kinetic analysis, and emission spectroscopic measurements. In plasma CO2 hydrogenation over Pd/ZnO, the hydrogenation of adsorbed surface CO2 on Pd/ZnO is the dominant reaction route for the enhanced CO2 conversion, which can be ascribed to the generation of a ZnOx overlay as a result of the strong metal–support interactions (SMSI) at the Pd–ZnO interface and the presence of abundant H species at the surface of Pd/ZnO; however, this important surface reaction can be limited in the Plasma + ZnO system due to a lack of active H species present on the ZnO surface and the absence of the SMSI. Instead, CO2 splitting to CO, both in the plasma gas phase and on the surface of ZnO, is believed to make an important contribution to the conversion of CO2 in the Plasma + ZnO system.
研究领域:
催化化学
·
等离子体化学
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环境科学
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可持续能源
✓ 已验证
产品关联
DOI
PubMed
JOURNAL OF THE ENERGY INSTITUTE
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2024
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IF 5.6
Zheng Bo,Mengyu Cao,Yaolin Wang,Jianhua Yan,Kefa Cen,Xin Tu
Plasma catalytic CO 2 hydrogenation has emerged as a promising approach for converting CO 2 into valuable chemicals such as CO, offering a potential solution to mitigate greenhouse gas emissions. In this study, we investigate the synergistic effect between plasma and a Cu/Ti 3 C 2 T x MXene catalyst for CO 2 hydrogenation via the reverse water gas shift (RWGS) reaction in a dielectric barrier discharge (DBD) reactor. Our findings reveal a significant enhancement in CO 2 conversion (33.1%) and CO yield (31.9%) when using the Cu/Ti 3 C 2 T x catalyst compared to plasma alone or with a Ti 3 C 2 T x foam. Plasma treatment creates unsaturated Ti sites on the Ti 3 C 2 T x surface, dramatically improving CO 2 adsorption and activation, while Cu nanoparticles significantly enhances the activation and dissociation of H 2 molecules on the catalyst surface. These surface adsorbed hydrogen species readily hydrogenate adsorbed CO 2 molecules through the Langmuir-Hinshelwood mechanism. Furthermore, these surface hydrogen species can also participate in the conversion of gas-phase CO 2 molecules through the Eley-Rideal pathway. This work sheds light on the synergistic plasma catalytic mechanism and provide insights for optimizing CO 2 hydrogenation processes using MXene catalysts.
研究领域:
化学工程
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催化
·
环境科学
·
等离子体化学
✓ 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）