FUEL PROCESSING TECHNOLOGY
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2023
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IF 7.5
Saisai Liu,Jing Liu,Guanyi Chen,Jingang Yao,Beibei Yan,Weiming Yi,Zhanjun Cheng,Chunyan Tian,Huijie Zao
Syngas is a key precursor for synthesizing gasoline (C 5 -C 11 ) hydrocarbons, offering an efficient route for utilizing non-petroleum carbon sources. However, the conventional Fischer-Tropsch synthesis (FTS) process faces a constraint with a maximum 45% selectivity for C 5 -C 11 , attributed to the Anderson-Schultz-Flory (ASF) distribution. Herein, bifunctional catalysts comprising ZnZrO x with different Zr/Zn ratios along with SAPO-11 zeolite sieves featuring varied morphologies like nanosheets (SA-A), petals (SA-B), and spheres (SA-C) have been effectively formulated and employed for the syngas-to-gasoline hydrocarbons (STG) reaction. Notably, the selectivity toward C 5 -C 11 far exceeded the ASF limits. Under identical reaction parameters, the Zn 1 Zr 4 O x /SA-A catalyst demonstrated notable enhancements of 6.6% and 26.2% in CO conversion, along with 4.6% and 7.6% increases in C 5 -C 11 selectivity, as compared to that of Zn 1 Zr 4 O x /SA-B and Zn 1 Zr 4 O x /SA-C catalysts, respectively. Furthermore, under the ideal conditions (380 °C, 4.5 MPa and gas hourly space velocity (GHSV) of 2400 mL min −1 g −1 ), Zn 1 Zr 4 O x /SA-A exhibited an exceptional C 5 -C 11 selectivity of 69.8% (CO 2 -free) alongside a single-pass CO conversion of 30.4%. Impressively, isoparaffin constituted 39.2% of the total composition , with the iso/n-paraffin ratio reaching 11.8. Even after 100 h, the catalyst maintained its remarkable catalytic activity , with the CO conversion and C 5 -C 11 selectivity maintaining levels of 27.5% and 66.85%, respectively.
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
ACS Sustainable Chemistry & Engineering
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2021
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IF 8.198
Wen Li,Kuncan Wang,Guowu Zhan,Jiale Huang,Qingbiao Li
Transformation of CO2 with the help of green hydrogen (prepared from renewable energy) into valuable light olefins (C2=–C4=) is a promising route for utilizing the carbon resource in CO2. Currently, most of the reported bifunctional catalysts for CO2 hydrogenation to light olefins follow a methanol-mediated route that adopts SAPO-34 as the zeolite component. Although ZSM-5 has been widely used in the methanol to propylene process using fixed bed reactors due to high shape-selective property and long lifetime, ZSM-5-based bifunctional catalysts have seldomly been used for CO2 hydrogenation to light olefins. Herein, we proposed a novel synthetic strategy for bio-ZSM-5 with mild acid strength and relatively low acid density using the natural rice husk as a template. The bio-ZSM-5 was integrated with ZnZrOx solid solution nanoparticles, and the derived ZnZrOx&bio-ZSM-5 catalysts exhibited a high C2=–C4= selectivity of 64.4% and total C2–C4 selectivity of 94.5%, but relatively low CH4 selectivity (5.5%) and aromatic selectivity (<1%). The post-modified ZnZrOx&bio-ZSM-5 catalysts further enhanced the catalytic stability with less coke deposition and regulated the ethylene to propylene ratio in light olefin distribution. Furthermore, *CHxO was found to be the key intermediate formed on the ZnZrOx surface and was transferred to the Brønsted acid sites in the bio-ZSM-5 for the subsequent conversion to light olefins, as confirmed by in situ DRIFTS and chemical trapping mass spectrometry.
研究领域:
催化化学
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环境科学
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材料科学
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DOI
高影响因子
ACS Applied Nano Materials
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2024
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IF 5.3
Jialing Song,Bin Chen,Juanjuan Bian,Yanmei Cai,Sajid Ali,Dongren Cai,Bingyun Zheng,Jiale Huang,Guowu Zhan
ZnZrOx solid solution is a promising catalyst for the hydrogenation of CO2 to methanol, but precise design of the nanostructure to enhance catalytic performance remains a significant challenge. Herein, a ZnZrOx-based solid solution (ZnZrOx-MD) nanoparticle catalyst with uniform metal dispersion and remarkable CO2 activation ability was developed via calcination of metal–organic frameworks [MOFs, viz., PCN-223(Zn)] with mixed metal (Zr and Zn) as solid precursors. It was found that the ZnZrOx-MD nanoparticle catalyst outperformed its counterparts prepared using a traditional deposition–precipitation method (ZnZrOx-TD). Furthermore, the effects of the micromorphology and crystal composition on the catalytic performance of ZnZrOx-MD were systematically investigated. Comprehensive characterization results reveal that ZnZrOx-MD contained abundant oxygen vacancies, large specific surface area, and uniform metal dispersion, which collectively contributed to its excellent CO2 hydrogenation performance, resulting in a high methanol selectivity of 77.2% at 320 °C. In situ DRIFTS experiments confirm the mechanism for the CO2 hydrogenation to methanol over the ZnZrOx nanoparticle catalysts involved the initial formation of HCOO* species, followed by subsequent hydrogenation to generate CH3O* and ultimately produce methanol. Overall, this work highlights the potential benefits of MOFs as thermal decomposition precursors for the fabrication of solid-state catalysts with unique properties.
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
CHEMICAL ENGINEERING JOURNAL
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2025
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IF 13.2
Lingxi Bai,Haonan Li,Xingxiang Wang,Xin Pu,Zhipeng Lin,Shuzhen Zhou,Jiangbing Li,Xiaogang Wang,Jie Li,Lingtao Kong,Lanli Bai,Jichang Liu
Biomass valorization plays a vital role in ecological conservation and the advancement of a circular economy, while posing significant scientific challenges. This work successfully constructed a novel tandem catalytic system (ZnZrOx-ZSM-5) for the efficient production of sustainable monocyclic aromatics (SMAs) via the ex-situ catalytic pyrolysis of cotton stalk. Compared to the sole ZSM-5, the tandem catalyst significantly enhanced the absolute yield of SMAs from 8.2 % to 26.8 %. Combined various structural characterization and carefully catalytic experiments, it was revealed that pyrolysis volatiles derived from cotton stalk first encounter the ZnZrOx bed-rich in oxygen vacancies and basic sites, where compounds such as AAAKs (alcohols, aldehydes, acetic acid, and ketone) and bulky alkoxy-phenols are preferentially pre-cracked into alkanes/alkenes and light phenols, respectively. Subsequently, within the ZSM-5 bed, these pre-cracked intermediates enhance the formation of SMAs by a series of reactions-including Diels-Alder condensation, dehydroxylation, and aromatization with hydrocarbon pool species. Simultaneously, GC‑MS analysis confirmed that the introduction of ZnZrOx effectively suppresses the formation of bulky polycyclic molecules (e.g., naphthalene, phenanthrene), thereby alleviating catalyst pore blockage and deactivation.
研究领域:
生物质转化
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催化化学
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能源化工
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环境科学
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绿色化学
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可再生能源
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
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IF 21.1
Mengyuan Zhang,Li Zhang,Jian Ye,Hailong Li,Ying Qu,Chuandong He,Qiang Niu,Pengfei Zhang
ZnZrO x was a potential catalyst for CO 2 hydrogenation to methanol. However, the micrometer bulky morphology and low surface areas (e.g., <10 m 2 g -1 ) by traditional synthesis methods obstructed their way. This work demonstrated the electrospinning method for fabricating ZnZrOx nanofibers, with 30ZnZrOx-ES showing a significantly higher specific surface area (113.5 m²/g). The CH₃OH yield of 30ZnZrOx-ES was 1.6 times higher than that of 30ZnZrOx-CP, with good stability over 600 hours (300°C, 5 MPa, GHSV = 24,000 mL g⁻¹ h⁻¹). In situ infrared spectroscopy indicated that 30ZnZrO x -ES was easier to produce formates than 30ZnZrO x -CP. DFT calculations and experimental results (EPR, Raman) confirmed that the oxygen-rich surface with abundant oxygen vacancies would enhance H₂ activation of 30ZnZrOx-ES.
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高影响因子
Journal of Environmental Chemical Engineering
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2026
·Vol. 14
·期 1
·121143
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IF 7.2
Rui Xiang,Tao Du,He Jia,Yingnan Li,Peng Chen,Qiang Yue,Heming Wang,Yisong Wang
Global warming caused by CO 2 has drawn increasing attention in recent years. Direct hydrogenation of carbon dioxide to light olefins (C 2 = -C 4 = ) is considered a promising strategy for carbon reduction. However, the catalytic performance of metal oxide/zeolite bifunctional catalysts still requires further optimization to enhance CO 2 conversion efficiency and C 2 = -C 4 = selectivity. This study incorporates a hierarchical porous structure into SAPO-34 molecular sieves to modulate their pore channel structure, while Mg doping is introduced into ZnZrOₓ to improve its crystal structure. Characterization results, including NH 3 -TPD and CO 2 -TPD, reveal that structural modifications improve the acidity of the SAPO-34 molecular sieve and enhance the CO 2 adsorption and activation capacity of ZnZrO x . The catalytic performance of the Z/S bifunctional catalyst was evaluated under the following reaction conditions: mass ratio of ZnZrO x to SAPO-34 (Z:S) = 1:1, reaction temperature = 380°C, reaction pressure = 2 MPa, and gas hourly space velocity (GHSV) = 16,000 mL·g cat ⁻¹ ·h⁻¹ . The bifunctional catalyst, composed of ZnZrO x doped with 3 % Mg and SAPO-34 with a mesoporous structure, demonstrated a CO 2 conversion of 10.7 % and a C 2 = -C 4 = selectivity of 78.8 % under these conditions, outperforming other Z/S catalysts. This work offers both theoretical and experimental insights for the design of highly efficient bifunctional catalysts for CO 2 hydrogenation to C 2 = -C 4 = .
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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
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
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高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2026
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IF 6.7
Huayuying Peng,Fei Liu,Shangyan Zhou,Xinyi Ran,Xiaodan Wang,Mengqing Yao
Metal promotion is a common strategy to improve the hydrogenation activity of oxide catalysts. However, its efficacy is frequently hindered by insufficient hydrogen supply to active sites and the tendency of metal dopants to sinter under high-temperature conditions. Herein, we design a Cu-MXene/ZnZrO x composite catalyst, in which Ti vacancies within the MXene framework anchor Cu, enabling efficient hydrogen activation and subsequent spillover to ZnZrO x . In comparison with the conventional Cu/ZnZrO x catalyst, the Cu-MXene/ZnZrO x structure not only enhances the resistance of Cu species to high-temperature sintering but also significantly promotes the kinetics of hydrogen transfer. Additionally, this structural design facilitates the generation of a higher density of oxygen vacancies (OVs). As expected, the Cu-MXene/ZnZrO x catalyst demonstrates outstanding performance, achieving 12.3% CO 2 conversion and 91.2% methanol selectivity—exceeding all previously reported ZnZrO x -based systems. Density functional theory (DFT) calculations and Diffused reflectance infrared fourier transform spectroscopy (DRIFTS) indicate that atomically dispersed Cu sites facilitate H 2 dissociation, while the Cu-MXene interface promotes rapid H spillover to neighboring Zn-Zr sites, enhancing electron transfer and CO 2 reduction kinetics, thereby forming abundant active intermediates of HCOO* and CH 3 O*. This study offers a robust and scalable approach for developing highly efficient catalysts for CO 2 -to-methanol conversion.
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高影响因子
ACS Catalysis
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2025
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IF 13.1
Zhiwei Liang,Shan Tang,Siyu Chen,Lanqi Ning,Jijie Wang,Can Li
Zinc–zirconium oxides (ZnZrOx) are highly selective and stable catalysts for the hydrogenation of CO2 to CH3OH. However, their catalytic activity has remained relatively moderate, and the influence of the ZnZrOx crystalline phase on performance is not yet fully elucidated. Here, we report a mixed-phase ZnZrOx, comprising coexisting tetragonal and monoclinic domains, and correlate this biphasic architecture with the catalytic performance. At 320 °C, the mixed-phase ZnZrOx catalyst delivers a CO2 conversion of 9.2% coupled with an impressive CH3OH selectivity of 87%, representing a 1.4-fold increase in conversion compared to its purely tetragonal counterpart while maintaining equivalent selectivity. In-depth characterizations attribute this improved performance primarily to the emergence of a two-phase interface, which enhances the dissociation and activation of H2. Density functional theory calculations further reveal that this interfacial region plays a vital role in promoting heterolytic H2 dissociation, boosting the formation of HCOO* and lowering the energy barriers of the rate-determining step for CH3OH formation. This work highlights the effectiveness of the crystal-phase architecture in optimizing ZnZrOx catalysts for CO2 hydrogenation to CH3OH, offering strategic insights for the design of advanced oxide-based hydrogenation systems.
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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物理化学
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环境科学
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高影响因子
JOURNAL OF CATALYSIS
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2021
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IF 7.92
Feng Sha,Chizhou Tang,Shan Tang,Qingnan Wang,Zhe Han,Jijie Wang,Can Li
Catalytic conversion of CO 2 into methanol utilizing green hydrogen produced from renewable energy is a promising route to realize carbon neutrality. Although ZnZrO x solid solution catalyst displays excellent catalytic performance, it is still highly desired to make any further improvement. Herein, we found the promoting effect of incorporating Ga into ZnZrO x solid solution catalyst in CO 2 hydrogenation to methanol. Ga promoted ZnZrO x (GaZnZrO x ) solid solution catalyst exhibits CO 2 conversion of 8.8% and methanol space time yield of 630 mg g cat −1 h −1 that are higher than those of ZnZrO x solid solution catalyst (7.7%, 556 mg g cat −1 h −1 ) at 320 °C, while the highly selectivity toward methanol remains unchanged. Chemisorption and H 2 -D 2 exchange results show that GaZnZrO x solid solution catalyst displays higher capacity for the adsorption and activation of H 2 than ZnZrO x solid solution catalyst. Electron paramagnetic resonance result suggests that more oxygen vacancies are derived after incorporating Ga into ZnZrO x solid solution catalyst. In situ diffuse reflectance infrared Fourier transform spectra indicate that the HCOO* and CH 3 O* species are the main intermediate species. The higher IR intensity of intermediate species and lower CH 3 O*/HCOO* ratio on GaZnZrO x solid solution catalyst suggest that the hydrogenation of HCOO* to CH 3 O* is boosted. These results reveal the promoting effect of incorporated Ga into ZnZrO x solid solution catalyst that improves the adsorption and activation of H 2 and CO 2 , thus enhancing catalytic performance of methanol synthesis from CO 2 hydrogenation.
研究领域:
催化化学
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能源科学
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产品关联
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高影响因子
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