Small
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2024
·
IF 13
Jun Deng,Limei Qiu,Mudi Xin,Wenhui He,Wenhui Zhao,Juncai Dong,Guangtong Xu
Cu-based metal-organic frameworks (MOFs) have attracted much attention for electrocatalytic CO 2 reduction to high value-added chemicals, but they still suffer from low selectivity and instability. Here, an associative design strategy for the valence and coordination environment of the metal node in Cu-based MOFs is employed to regulate the CO2 electroreduction to ethylene. A novel “reduction-cleavage-recrystallization” method is developed to modulate the Cu(II)-Trimesic acid (BTC) framework to form a Cu(I)-BTC structure enriched with free carboxyl groups in the secondary coordination environment (SCE). In contrast to Cu(II)-BTC, the Cu(I)-BTC shows higher catalytic activity and better ethylene selectivity (≈2.2-fold) for CO 2 electroreduction, which is further enhanced by increasing the content of free carboxyl groups, resulting in ethylene Faraday efficiency of up to 57% and the durability of the catalyst could last for 38 h without performance decline. It indicates that the synergistic effect between Cu(I)-O coordinated structure and free carboxyl groups considerably enhances the dimerization of *CO intermediates and hinders the hydrogenation of *CO intermediates in these competitive pathways. This work unravels the strong dependence of CO 2 electroreduction on the Cu valence state and coordination environment in MOFs and provides a platform for designing highly selective electrocatalytic CO 2 reduction catalysts.
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PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2024
·Vol. 121
·期 9
·e2315956121
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IF 9.4
Chenyu Du,Jianping Sheng,Fengyi Zhong,Ye He,Huiyu Liu,Yanjuan Sun,Fan Dong
Photo-catalytic CO2 reduction with perovskite quantum dots (QDs) shows potential for solar energy storage, but it encounters challenges due to the intricate multi-electron photoreduction processes and thermodynamic and kinetic obstacles associated with them. This study aimed to improve photo-catalytic performance by addressing surface barriers and utilizing multiple-exciton generation in perovskite QDs. A facile surface engineering method was employed, involving the grafting of ferrocene carboxylic acid (FCA) onto CsPbBr3 (CPB) QDs, to overcome limitations arising from restricted multiple-exciton dissociation and inefficient charge transfer dynamics. Kelvin Probe Force Microscopy and XPS spectral confirmed successfully creating an FCA-modulated microelectric field through the Cs active site, thus facilitating electron transfer, disrupting surface barrier energy, and promoting multi-exciton dissociations. Transient absorption spectroscopy showed enhanced charge transfer and reduced energy barriers, resulting in an impressive CO2-to-CO conversion rate of 132.8 μmol g−1 h−1 with 96.5% selectivity. The CPB-FCA catalyst exhibited four-cycle reusability and 72 h of long-term stability, marking a significant nine-fold improvement compared to pristine CPB (14.4 μmol g−1 h−1). These results provide insights into the influential role of FCA in regulating intramolecular charge transfer, enhancing multi-exciton dissociation, and improving CO2 photoreduction on CPB QDs. Furthermore, these findings offer valuable knowledge for controlling quantum-confined exciton dissociation to enhance CO2 photocatalysis.
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APPLIED CATALYSIS B-ENVIRONMENTAL
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2024
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IF 20.2
Yingnan Cao,Chi Zhang,Wenchao Wang,Yunni Liu,Ying Tao,Jinchen Fan,Ming Chen,Dieqing Zhang,Guisheng Li
Photo-assisted electrocatalytic (PAEC) CO 2 conversion is a crucial approach for achieving sustainable carbon neutrality. Here, we have developed a binary-junctions photoanode by integrating SrTiO 3 and anatase-rutile TiO 2 nanotube arrays (STO/A-R TNTAs), which exhibits exceptional activity and selectivity in converting CO 2 to HCOOH. The synergetic effects of the SrTiO 3 /TiO 2 heterogeneous junction and the anatase-rutile TiO 2 heterophase junction effectively facilitate photoelectron separation and storage, leading to a potential difference between anode and cathode. The establishment of the electron storage strategy, triggered by hetero- junction/phase interfaces, serves as remarkably efficient electron trapping regions with dam-like characteristics. As a result, the STO/A-R TNTAs achieves a generation rate of 68.24 μmol cm −2 h −1 with 92.25% selectivity and 90.70% Faradic efficiency. This performance is approximately 8 times higher compared to the pristine TiO 2 nanotube arrays photoanode. The implementation of the electron storage mechanism presents a promising approach to improve CO 2 reduction activity and selectivity.
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APPLIED CATALYSIS A-GENERAL
·
2025
·
IF 4.8
Jianhao Li,Zhicheng Hu,Shuhuan Han,Dapeng Cao,Xiaofei Zeng,Jianfeng Chen
Electrocatalytic CO 2 reduction reaction (CO 2 RR) to multi-carbon product, especially for ethylene (C 2 H 4 ), provides a favorable pathway for carbon neutrality and renewable energy storage. However, the second-order C-C coupling reactions in CO 2 RR need always the high activation/driven energy in dynamics originating from the trace C 1 intermediate product. Herein, we synthesized the Ag-decorated Cu 2 O porous hollow core-shell catalyst named Ag@Cu 2 O where Ag nanoparticles uniformly distributed on inner the surface of the hollow Cu 2 O (H-Cu 2 O) via the sacrificial template method. Benefiting from the synergistic hollow structure and electron transfer from Cu and Ag to O, Ag@Cu 2 O catalyst delivers the excellent C 2 H 4 Faradaic Efficiency (FE) of 55 % ± 2 % at −1.0 V (vs. RHE), which is superior to the most reported catalysts. More importantly, in situ infrared spectroscopy and density functional theory (DFT) calculations reveal the introduction of Ag can decrease the activation energy required for *CO and C-C coupling.
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2012
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IF 2.237
Fang-fang Tong,Hong Xu,Jian Yu,Li-xiong Wen,Jun Zhang,Jia-song He
A series of poly(methyl methacrylate) (PMMA)/1-dodecyl-3-methylimidazolium hexafluorophosphate ionic liquid ([C12MIM][PF6]) blends were prepared by melt blending. The compatibility of blends was verified by scanning electron microscopy and differential scanning calorimetry. The introduction of [C12MIM][PF6] decreased the glass transition temperature of the blends due to its plasticization effect and increased the diffusivity of CO2 without significantly affecting the CO2 solubility. These blends were foamed with supercritical CO2 as the blowing agent via a pressure-quenching process. The foaming conditions are divided into three regions according to the main morphological difference of foams. At relatively low temperatures and pressures, neat PMMA could not be foamed, while the addition of [C12MIM][PF6] facilitated the formation of cells. By increasing temperature or pressure, neat PMMA foams were obtained with wide cell size distribution, while the blend foams were formed with narrowed cell size distribution and increased cell size. At high temperatures and pressures, neat PMMA was foamed with narrow cell size distribution and high cell density, while the major effect of [C12MIM][PF6] was to increase the cell size. These results indicated that the plasticization effect and the low surface energy of [C12MIM][PF6] accounted for the differences on the cell morphology between neat PMMA and the blend foams.
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JOURNAL OF CHEMICAL AND ENGINEERING DATA
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2012
·
IF 1.693
Hai Zhang,Rulong Li,Baogen Su,Huabin Xing,Yiwen Yang,Qilong Ren
The triethylene glycol and tripropylene glycol derivatives terminated with the CO2-philic phosphoryl groups, named 2-(2-(2-((2-ethylhexoxy(methoxy)phosphoryl)oxy)ethoxy)ethoxy)ethyl 2-ethylhexyl methyl phosphate (EG3EH) and 2-(2-(2-((2-ethylhexoxy(methoxy)phosphoryl)oxy)propoxy)propoxy)propyl 2-ethylhexyl methyl phosphate (PG3EH), were synthesized and characterized. The solubilities of EG3EH and PG3EH in scCO2 were determined by a static method at temperatures from (313 to 333) K and over a pressure range of (10 to 19) MPa. The values calculated by the Bartle semiempirical model exhibited good agreement with the experimental data.
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ACS Nano
·
2024
·
IF 15.8
Chen Liao,Zhizhong He,Feng Wang,Ya Liu,Liejin Guo
Photocatalytic CO2 conversion is a promising approach to simultaneously mitigate climate change and alleviate the energy crisis. However, infrared light, which constitutes nearly half of the solar energy, has not been effectively utilized yet. In this work, we discover a photogenerated charge transition mechanism in CuInS2 with intrinsic InCu antisite defects for synergistic utilization of full-spectrum photons. Femtosecond transient absorption spectroscopy and DFT calculation unveil an intermediate band induced by the intrinsic antisite defects, where cascaded sub-band transition could be realized by high-energy photons (UV–vis) and low-energy (IR), thus improving the absorption range of infrared light as well as the utilization efficiency of photogenerated carriers. In situ Kelvin probe force microscopy demonstrates that the generation of photoexcited electrons could be greatly enhanced through this synergistic utilization of full spectrum light. Moreover, in situ X-ray photoelectron spectroscopy and in situ diffuse reflectance infrared Fourier transform spectroscopy reveal that infrared photons could also enhance the adsorption and activation of CO2 and H2O on the catalyst surface. As a result, the CO production rate under full spectrum light reaches 19.9 μmol g–1 h–1, which is more than a 7-fold increase over that under UV–vis irradiation.
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CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Hangzhi Wu,Shuyue Wen,Xiaomin Zhang,Shule Zhang,Xuefeng Guo,Youting Wu
Sterically hindered amines (SHAs), such as 2-amino-2-methyl-1-propanol (AMP), are an important subclass of conventional absorbents with large CO 2 capacity, while ionic liquids (ILs) are novel materials with unique physiochemical properties including negligible vapor pressure and high thermal stability. To combine the characteristics of these two kinds of CO 2 absorbents together, we proposed and successfully synthesized a series of new sterically hindered amino acid ionic liquids (SHAAILs). These SHAAILs (aqueous solutions) were proved to have excellent physiochemical properties, large CO 2 capacity (up to 0.92 mol mol −1 at 313.2 K, 1.0 bar), and fast absorption rate (greater than AMP). Dynamic absorption and thermal regeneration experiments were done to further illustrate the capability of SHAAILs in absorbing and desorbing CO 2 , and [N 1111 ][β-iPrNH-Ala] was found to be an excellent CO 2 absorbent owing to its suitable steric hinderance and also its ionic nature. NMR analysis confirms that the SHAAILs of suitable steric hinderance undergo the carbamate-mediated rapid hydrolysis mechanism in absorbing CO 2 . Due to the comprehensive advantages of SHAAILs, they are believed to have great potentials as efficient CO 2 absorbents in practical applications.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Changming Zhang,Rongxian Wang,Xiaochao Zhang,Zhiyan Dong,Wensheng Wu,Jinbo Xue,Caimei Fan
The efficient capture of CO 2 molecules is a crucial step in the light-driven CO 2 synthesis of high value-added products. In this work, CeO 2 is embedded in polyacrylonitrile-based carbon spheres (PANACSs) via a suspension polymerization and carbonization method to synthesise CeO 2 @PANACSs with bifunction (CO 2 adsorption and reduction ablity), and the strong oxidising capacity Bi 2 Fe 4 O 9 was coupled to obtain ternary Bi 2 Fe 4 O 9 /CeO 2 @PANACSs composites with high adsorption-reduction capacity for CO 2 . The effective synergistic effects between Bi 2 Fe 4 O 9 and CeO 2 @PANACSs realize that the CO yield of ternary hybrid photocatalyst can reach as high as 256.1 μmol g −1 for 10 h, approximately 19.55 times, 1.45 times and 1.62 times higher than that of pristine PANACSs, Bi 2 Fe 4 O 9 and CeO 2 , respectively. The exceptional performance of Bi 2 Fe 4 O 9 /CeO 2 @PANACSs composites is mainly attributed to the synergistic effect of the ternary system, which not only provides CO 2 -rich adsorption-reduction active sites but also effectively inhibits photogenerated electron-hole complexation. Meanwhile, the outer layer of Bi 2 Fe 4 O 9 with its excellent oxidising capacity also provides a large amount of H* to ensure efficient hydrodeoxygenation of CO 2 . Finally, combined with the results of in situ fourier transform infrared spectra, a possible mechanism for the photocatalytic reduction of CO 2 over ternary photocatalysts is proposed. Our finding provides a noteworthy promising strategy to construct bifunctional composite photocatalysts for achieving the high-efficient CO 2 adsorption and photoreduction to CO.
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Journal of Materials Chemistry A
·
2025
·
IF 9.5
Shuai Liu,Dicka Ar Rahim,Yan Zhang,Dan Wang,Ekkachai Kanchanatip,Yi He,Mi Yan
To advance the utilization of high-concentration CO2 produced in biogas upgrading, it is essential to remove associated hydrogen sulfide (H2S). This study presents a series of bimetallic Fe–Cu oxides supported on multi-walled carbon nanotubes (MWCNTs), which were synthesized to efficiently remove H2S from CO2-rich gas at low temperatures. The synergy of the bimetallic elements not only forms a multifaceted active phase but also causes new defects on the MWCNTs, creating more H2S/CO2 separation sites. The adsorption experiments demonstrate that the deep H2S removal performance of the adsorbent is unaffected by the CO2 concentration, achieving a maximum adsorption capacity of 30.11 mg g−1, which exceeds that of commercial desulfurizers and previously reported adsorbents. Additionally, density functional theory calculations were employed to elucidate that the introduction of Cu species increases the gap in the average adsorption energies between H2S and CO2. The adsorbent also exhibited stability after 4-cycle regeneration at room temperature, maintaining 62.6% of its initial H2S capacity. This work underscores the potential of Fe–Cu oxide/MWCNTs adsorbents as a viable, regenerable solution for H2S removal in CO2 purification, offering implications for carbon-negative construction.
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Inorganic Chemistry Frontiers
·
2024
·Vol. 11
·期 18
·6044-6051
·
IF 6.1
Kunhong Li,Yumei Hong,Xinyi Ma,Yujie Zhao,Shihao Zhang,Pengtao Ma,Jingyang Niu,Jingping Wang
Photocatalytic carbon dioxide reduction is considered an important strategy to solve environmental problems, such as greenhouse gases, but designing and synthesizing effective photocatalysts is a challenge. In recent years, photocatalytic carbon dioxide reduction by polyoxometalates (POMs) has attracted increasing research interest. Herein, the first purely inorganic ruthenium–germanium–molybdenum–oxygen cluster, Na12Rb2[Ru2O2(GeMo10O36)2]·44H2O (Ru2Ge2Mo20), was synthesized by hydrothermal and volatilization methods and applied to photocatalytic carbon dioxide reduction. The yield of CH4 reached 547.84 μmol g−1 in the heterogeneous photocatalytic reaction system with an electron selectivity of 96.86% with respect to CO (71.08 μmol g−1) after 6 h. The reaction mechanism was confirmed by UV-Vis diffuse reflection spectroscopy, ultraviolet photoelectron spectroscopy (UPS), electrochemical measurements, and steady-state fluorescence quenching experiments. This work provides a reference for the design of Ru-containing polyoxometalates for photocatalytic CO2 reduction.
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APPLIED CATALYSIS A-GENERAL
·
2017
·
IF 4.339
Yuan Ma,Ci Chen,Tengfei Wang,Jingshun Zhang,JiaJia Wu,Xiangdong Liu,Tiegang Ren,Li Wang,Jinglai Zhang
The efficient fixation of CO 2 without co-catalyst and solvent under metal-free condition is still an urgent topic in sustainable chemistry. In this work, a series of dialkylpyrazolium ionic liquids are employed to promote the cycloaddition of CO 2 and PO to produce PC. They would be easily synthesized by a simple one-pot reaction. The effect of alkyl chain length in cation and different anion is explored. Diethylpyrazolium iodide presents the excellent catalytic activity with the product yield of 96% and selectivity of 99% in a benign condition. Moreover, the catalyst could be reused for at least five times without significant loss of catalytic activity. An intensive structure-activity research testifies that the cycloaddition of CO 2 with PO is activated by a synergistic effect from both cation and anion of ILs. To confirm it, the detailed mechanism is investigated by density functional theory associated with the non-covalent interactions and atoms in molecule analysis. Besides the electrostatic interaction between cation of ionic liquid and PO, the noncovalent interaction, especially for hydrogen bond, plays a vital role in promoting the reaction.
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