APPLIED CATALYSIS B-ENVIRONMENTAL
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2022
·
IF 24.319
Wenhui Li,Xiaowa Nie,Hong Yang,Xiang Wang,Felipe Polo-Garzon,Zili Wu,Jie Zhu,Jianyang Wang,Yi Liu,Chuan Shi,Chunshan Song,Xinwen Guo
Efficient conversion of CO 2 is of great significance for sustainable supply of chemicals and fuels. While Co-based catalysts are known to be effective for CO hydrogenation in Fischer-Tropsch synthesis, they work very differently in CO 2 hydrogenation. This study reveals a crystallographic dependence of reaction pathways for CO 2 hydrogenation on Co catalyst showing a new type of structure sensitivity and structure-activity-selectivity relationship for CO 2 conversion to chemicals and fuels. The experimental work on CO 2 conversion including steady-state isotopic transient kinetic analysis (SSITKA) using 13 C-labeled CO 2 shows a preferential CH 4 formation over HCP-Co but dominant CO formation over FCC-Co. The density functional theory calculations indicate that CO 2 does dissociate directly into chemisorbed CO* and O* on both HCP-Co and FCC-Co, but the CO* intermediates on HCP-Co prefer to be hydrogenated to form CH 4 whereas the CO* on FCC-Co preferentially desorb to form CO. The significantly altered adsorption strength of CO* due to the presence of chemisorbed O* and CO 2 * species on the catalyst surface is responsible for the mechanistic disconnection in product selectivity between the CO 2 and CO hydrogenation over Co catalysts. This study also shows that the addition of K to Co diminishes the direct impact of Co crystal structure, but improves the selectivity to C 2 + hydrocarbons along with higher CO 2 conversion. This seems to result from another pathway originating from HCOO* intermediate from bonding interaction of surface Co atoms with carbon in CO 2 , leading to the formation of CH x * whose coupling subsequently give rises to C 2 + products. The present study sheds new light into the crystallographic structural sensitivity of CO 2 hydrogenation towards the rational design of more selective catalysts for CO 2 conversion.
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CHEMICAL ENGINEERING JOURNAL
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2022
·
IF 16.744
Menglei Mao,Tingting Zhai,Lingding Meng,Zihui Meng,Wenfang Liu
Enzymatic conversion of CO 2 to high-value chemicals is a significant route for the utilization of greenhouse gases in mild, high-selectivity and environment-friendly way, however, conversion efficiency is not yet satisfying. Here, mesoporous silica (mSiO 2 ) nanoparticles with controllable structure were prepared and modified by polydopamine (PDA) and polyethyleneimine (PEI), which were then used in an integrated process for CO 2 capture and conversion to formate for the first time. The effects of structure parameters of mSiO 2 and modification conditions on its application properties were investigated. The results show that in a range of 230 ∼ 500 nm, SiO 2 particles with smaller size exhibited better intensifying effect, while the optimal size was 410 nm for mSiO 2 with the same etching extent, attributed to a higher specific surface area. mSiO 2 itself was a robust CO 2 adsorbent and the addition of 0.01 g mSiO 2 (410) enabled CO 2 conversion to be accelerated 11.94 times compared to free enzyme. After modification, with 0.05 g PDA/PEI-mSiO 2(340) and PDA/PEI-mSiO 2(410) , the enzyme reaction was expedited up to 24 and 30.8 times of the system without particles due to an enhanced CO 2 uptake, as a collaborative result of mesoporous structure and amino-functionalization. Following that, PDA/PEI-mSiO 2(410) was used as the carrier for the co-immobilization of formate dehydrogenase and carbonic anhydrase, which could retain 86.7% activity after use for 10 times and 55.2% activity after 21 days at 4 °C, while 29.6% for free enzymes.
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Materials Research Express
·
2022
·Vol. 9
·期 1
·015504
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IF 2.025
Xiangwei Liu,Qian Ao,Shengyou Shi,Shuie Li
The existing CO2 absorption by deep eutectic solvents is limited by the unavoidable water absorption problem during use. In this study, we prepared three deep eutectic solvents with different alcohol aminations and added different water contents to discuss the effect of water content on the absorption of carbon dioxide by deep eutectic solvents. All deep eutectic solvents have a low melting point at room temperature as a liquid and have high thermal stability, where the choline chloride-diethanolamine deep eutectic solvents have a high viscosity. Anhydrous choline chloride-monoethanolamine deep eutectic solvents have the largest CO2 absorption, reaching 0.2715 g g−1, and the absorption of CO2 by anhydrous choline chloride-N-methyldiethanolamine deep eutectic solvents is only 0.0611 g g−1. Water content inhibited the absorption of CO2 in primary amine and secondary amine systems, whereas it enhanced the absorption of CO2 in tertiary amine systems, which was related to the reaction process of deep eutectic solvent and CO2.
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Carbon Letters
·
2022
·Vol. 32
·期 3
·807-814
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IF 3.117
Ning Hui,Guo Zhihao,Wang Wenhang,Wang Xiaoshan,Yang Zhongxue,Ma Zhengguang,Tian Yangming,Wu Chenghao,Hao Jian,Wu Mingbo
Electrochemical reduction of carbon dioxide to valuable chemicals is a promising way of storing renewable energy through electric-to-chemical energy conversion, while its large-scale application is in urgent need of cheap and high-performance catalysts. Herein, we invent a convenient method to synthesize N-doped porous carbon by ammonia etching the pyrolysis carbon of petroleum pitch. We found the ammonia etching treatment not only increase the pyridinic-N content, but also enlarge the specific surface area of the petroleum pitch-based porous carbon. As a cheap and easily available catalyst for carbon dioxide electroreduction, up to 82% of Faradaic efficiency towards carbon monoxide was obtained at − 0.9 V vs the reversible hydrogen electrode in 0.1 M KHCO 3 . After a long time electrocatalysis of more than 20 h, the Faradaic efficiency of carbon monoxide remains 80%, indicating the porous carbon as made have an ultra-high stability as catalyst for carbon dioxide reduction. Our work provides a new technology to economically prepare efficient electrocatalysts for carbon dioxide reduction.
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ChemSusChem
·
2022
·Vol. 15
·期 7
·e202200184
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IF 9.14
Siyong Ou,Min Zhou,Wen Chen,Yuyao Zhang,Yueli Liu
Graphical Photocatalytic CO 2 reduction : A COF-5/CoAl-layered double hydroxide (LDH) heterojunction photocatalyst is developed for the CO 2 reduction reaction. CoAl-LDH incorporation enhances the visible-light response-ability of the photocatalyst and improves the separation efficiency of photogenerated electron–hole pairs through the role of a type-II heterojunction. Photocatalytic conversion of CO 2 into value-added chemical fuels is an attractive route to mitigate global warming and the energy crisis. Reasonable design of optical properties and electronic behavior of the photocatalyst are essential to improve their catalytic activity. Herein, the 1D/2D heterojunction by direct in-situ synthesis of the covalent organic framework (COF)-5 colloid on the surface of CoAl layered double hydroxide (LDH) was used as the prospective photocatalyst for CO 2 reduction. COF-5/CoAl-LDH nanocomposite achieved 265.4 μmol g −1 of CO with 94.6 % selectivity over CH 4 evolution in 5 h under visible light irradiation, which was 4.8 and 2.3 times higher than those of COF-5 colloid and CoAl-LDH, respectively. The enhanced catalytic activity was derived from the increased visible-light activity and the construction of type II-2 heterojunction, which greatly optimized visible light harvesting and accelerated the efficient separation of the photoinduced holes and electrons. This work paves the way for rational design of heterojunction catalysts in photocatalytic CO 2 reduction.
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CHEMICAL ENGINEERING SCIENCE
·
2022
·
IF 4.889
Pan Ma,Meili Ding,Xi Liu,Wei Rong,Jianfeng Yao
Metal-organic framework (MOF) derived porous carbons are known as desirable catalysts for carbon dioxide (CO 2 ) catalytic conversion. However, practical CO 2 utilization processes are severely hampered by their powder form and relatively poor activities. Herein, we demonstrate the rational synthesis of ZnO and/or metallic Co embedded in N-doped porous carbon by one-step pyrolysis of bimetallic MOF, Co/Zn-ZIF. The optimized catalyst exhibits remarkable activity and recyclability towards the coupling reaction of CO 2 and epoxides owing to hierarchical pore, good CO 2 uptake and sufficient active sites. More importantly, its catalytic performance can be well maintained even under dilute CO 2 (15%), humid environment or light irradiation instead of heating. These results pave a way to develop highly efficient materials for practical CO 2 catalytic conversion.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2022
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IF 4.326
Wei Guo,Huanhao Chen
Nonthermal plasma (NTP)-assisted CO2 methanation can activate and convert stable CO2 molecules under ambient conditions as compared to conventional thermal catalysis (normal operation temperature up to 450 °C), which is a good technique to reduce CO2 emissions and simultaneously utilize the renewable energies like solar and wind. It is critical to develop a robust catalyst with good catalytic performance in order to make NTP catalytic CO2 methanation more competitive. Herein, we present a simple yet efficient synthesis of CeO2-supported Ni catalysts with yttrium (Y) as the promoter (i.e., Ni–Y/CeO2) via mechanochemical synthesis for efficient NTP catalytic CO2 methanation. The developed 7.5Ni–1Y/CeO2 catalyst demonstrated the highest energy efficiency values for CO2 conversion and CH4 yield, i.e., ∼57 gCO2 kWh–1 and ∼17 gCH4 kWh–1, respectively. The CO2-TPD and HRTEM results confirmed that the doped Y positively enhanced the basicity of the catalysts and also decreased the particle size of Ni nanoparticles, thus promoting the NTP catalytic activity of CO2 methanation. The catalyst displayed excellent short-term stability for plasma catalytic CO2 methanation over a 12 h on-stream evaluation, showing a CO2 conversion of 84.2 ± 1.8% and a CH4 selectivity of 83.3 ± 1.9%.
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Nature Communications
·
2022
·Vol. 13
·期 1
·1-10
·
IF 17.694
Zhou Jun,Gao Zhe,Xiang Guolei,Zhai Tianyu,Liu Zikai,Zhao Weixin,Liang Xin,Wang Leyu
Supports can widely affect or even dominate the catalytic activity, selectivity, and stability of metal nanoparticles through various metal-support interactions (MSIs). However, underlying principles have not been fully understood yet, because MSIs are influenced by the composition, size, and facet of both metals and supports. Using Ru/TiO 2 supported on rutile and anatase as model catalysts, we demonstrate that metal-support interfacial compatibility can critically control MSI modes and catalytic performances in CO 2 hydrogenation. Annealing Ru/rutile-TiO 2 in air can enhance CO 2 conversion to methane resulting from enhanced interfacial coupling driven by matched lattices of RuO x with rutile-TiO 2 ; annealing Ru/anatase-TiO 2 in air decreases CO 2 conversion and converts the product into CO owing to strong metal-support interaction (SMSI). Although rutile and anatase share the same chemical composition, we show that interfacial compatibility can basically modify metal-support coupling strength, catalyst morphology, surface atomic configuration, MSI mode, and catalytic performances of Ru/TiO 2 in heterogeneous catalysis.
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ChemSusChem
·
2022
·Vol. 15
·期 8
·e202200090
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IF 9.14
Wenwen Bao,Senhe Huang,Diana Tranca,Boxu Feng,Feng Qiu,Fermín Rodríguez-Hernández,Changchun Ke,Sheng Han,Xiaodong Zhuang
Graphical Beauty in balanced asymmetry : An asymmetric Co II porphyrin ( as -PorCo) is constructed with a substituent of 2,6-dimethylbenzene to enhance the charge transfer capability from carbon nanotubes to as -PorCo, resulting in large partial current density of 8 mA cm −2 and high turnover frequency of 5656 h −1 at −0.7 V vs. reversible hydrogen electrode in aqueous solution. The present study provides the new insight into molecular design of catalysts for efficient electrochemical CO 2 reduction. The electrochemical reduction of carbon dioxide (CO 2 ) based on molecular catalysts has attracted more attention, owing to their well-defined active sites and rational structural design. Metal porphyrins (PorMs) have the extended π-conjugated backbone with different transition metals, endowing them with unique CO 2 reduction properties. However, few works focus on the investigation of symmetric architecture of PorMs as well as their aggregation behavior to CO 2 reduction. In this work, a series of Co II porphyrins (PorCos) with symmetric and asymmetric substituents were used as model of molecular catalysts for CO 2 reduction. Owing to the electron donating effect of 2,6-dimethylbenzene (DMB), bandgaps of the complexes became narrower with the increasing number of DMB. As electrocatalysts, all PorCos exhibited promising electrocatalytic CO 2 reduction performance. Among the three molecules, asymmetric Co II porphyrin ( as -PorCo) showed the lowest onset potential of −288 mV and faradaic efficiencies exceeding 93 % at −0.6 V vs. reversible hydrogen electrode, which is highly competitive among the reported state-of-art porphyrin-based electrocatalysts. The CO 2 reduction performance depended on π-π stacking between PorCo with carbon nanotubes (CNTs) and adjacent PorCos, which could be readily controlled by atomically positioned DMB in PorCo. Density functional theory calculations also suggested that the charge density between PorCo and CNT was highest due to the weak steric hindrance in as -PorCo, providing the new insight into molecular design of catalysts for efficient electrochemical CO 2 reduction.
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JOURNAL OF CATALYSIS
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2022
·
IF 8.047
Yi Liu,Ying Chen,Yunli Liu,Zewen Chen,Huan Yang,Zhongxiao Yue,Qing Fang,Yunfei Zhi,Shaoyun Shan
Solar energy is considered as the cleanest, cheapest, and most sustainable energy source, and CO 2 cycloaddition that is drove by solar energy has unique advantages in the aspect of energy and environmental. Therefore, Zn and N co-doped porous carbon nanosheets (ZNCs), which were synthesized by a simple one-step pyrolysis method, as catalysts and photothermal material to photothermally drive cycloaddition of CO 2 . The prepared ZNCs show graphene-like layered structure, uniformly distributed Lewis acid (Zn atoms) sites and Lewis base (N atoms) sites, full spectrum absorption and high photothermal conversion efficiency. More importantly, ZNCs have a higher catalytic efficiency than traditional heating methods because it can be quickly in-situ heated by light, hence the yield of cyclic carbonate reached 91.1% (0.1 MPa CO 2 , 1000 mW·cm −2 full-spectrum irradiation, 12 h). ZNCs were recycled five times without significant reduction in catalytic efficiency, and have high activity to other series of epoxides. A possible CO 2 cycloaddition mechanism which is catalyzed by ZNCs is proposed, including the step of adsorption, ring opening, insertion and cyclic carbonates formation.
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National Science Review
·
2023
·Vol. 11
·期 2
·
IF 20.6
Du Xiaowei,Zhang Peng,Zhang Gong,Gao Hui,Zhang Lili,Zhang Mengmeng,Wang Tuo,Gong Jinlong
Gas diffusion electrodes (GDEs) mediate the transport of reactants, products and electrons for the electrocatalytic CO2 reduction reaction (CO2RR) in membrane electrode assemblies. The random distribution of ionomer, added by the traditional physical mixing method, in the catalyst layer of GDEs affects the transport of ions and CO2. Such a phenomenon results in elevated cell voltage and decaying selectivity at high current densities. This paper describes a pre-confinement method to construct GDEs with homogeneously distributed ionomer, which enhances mass transfer locally at the active centers. The optimized GDE exhibited comparatively low cell voltages and high CO Faradaic efficiencies (FE > 90%) at a wide range of current densities. It can also operate stably for over 220 h with the cell voltage staying almost unchanged. This good performance can be preserved even with diluted CO2 feeds, which is essential for pursuing a high single-pass conversion rate. This study provides a new approach to building efficient mass transfer pathways for ions and reactants in GDEs to promote the electrocatalytic CO2RR for practical applications.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Ruijie Chen,Lei Wang,Jing Ding,Jinfeng Zhang,Hui Wan,Guofeng Guan
Photocatalytic CO 2 reduction can simultaneously alleviate the energy crisis and solve environmental issues. Nevertheless, it is still challenging for designing photocatalysts with efficient carrier mobility in rational. Herein, the Bi 2 MoO 6 /g-C 3 N 4 (BMO/CN) heterostructure was constructed through a microwave-assisted which could enhance the construction of two-dimensional and two-dimensional (2D/2D) structures. The 2D/2D BMO/CN heterojunction possessed excellent charge separation efficiency which exhibited superior performance on photocatalytic CO 2 reduction. It was shown by the characterization that the (131) surface of Bi 2 MoO 6 was constructed with the (100) surface of g-C 3 N 4 . The work functions of Bi 2 MoO 6 and g-C 3 N 4 were determined to be 4.57 and 4.22 eV, respectively, which suggested the type-II heterojunction was formed. The formation of CO and CH 3 OH over the optimized BMO/CN-30% catalyst reached 2.44 and 3.61 µmol⋅g −1 ⋅h −1 , respectively. The immediate products of HCO 3 - were observed within in-situ FT-IR to further certify the evolution of CH 3 OH. This work highlighted a microwave-assisted strategy to build a heterojunction structure for enhancing photoreduction CO 2 .
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