APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
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IF 22.1
Tete Zhao,Xupeng Zong,Jiuding Liu,Jialei Chen,Keqiang Xu,Xiao Wang,Xijie Chen,Wutong Yang,Fangming Liu,Meng Yu,Fangyi Cheng
Copper-based nanomaterials are attractive in CO 2 electroreduction into valuable chemicals but still suffer from limited selectivity of C 2+ products due to the parasitic hydrogen evolution reaction and inefficient dimerization of absorbed CO intermediate (*CO). Herein, we report an in situ polymerization strategy to coat hydrophobic polymer containing methoxyl silane ((CH 3 O) 3 Si–) and trifluoromethyl (–CF 3 ) functional groups on Cu nanoparticles. The optimized Cu-poly exhibits a high Faradaic efficiency of 71.08 % and a remarkable partial current density of 355.4 mA cm −2 for C 2+ products in a membrane electrode assembly electrolyzer using a bicarbonate electrolyte. A combined study of density functional theory calculations and in situ infrared characterizations indicates that the enhanced performances could be ascribed to the decreased formation energy of *COCOH, induced by the withdraw-electron effect of –CF 3 and enhanced coverage of *CO. This work offers a new insight in tuning the electrocatalytic microenvironment through the surface polymerization process.
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Nature Communications
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2023
·Vol. 14
·期 1
·1-10
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IF 16.6
Qin Hai-Gang,Du Yun-Fan,Bai Yi-Yang,Li Fu-Zhi,Yue Xian,Wang Hao,Peng Jian-Zhao,Gu Jun
Electrochemical CO 2 reduction in acidic electrolytes is a promising strategy to achieve high utilization efficiency of CO 2 . Although alkali cations in acidic electrolytes play a vital role in suppressing hydrogen evolution and promoting CO 2 reduction, they also cause precipitation of bicarbonate on the gas diffusion electrode (GDE), flooding of electrolyte through the GDE, and drift of the electrolyte pH. In this work, we realize the electroreduction of CO 2 in a metal cation-free acidic electrolyte by covering the catalyst with cross-linked poly-diallyldimethylammonium chloride. This polyelectrolyte provides a high density of cationic sites immobilized on the surface of the catalyst, which suppresses the mass transport of H + and modulates the interfacial field strength. By adopting this strategy, the Faradaic efficiency (FE) of CO reaches 95 ± 3% with the Ag catalyst and the FE of formic acid reaches 76 ± 3% with the In catalyst in a 1.0 pH electrolyte in a flow cell. More importantly, with the metal cation-free acidic electrolyte the amount of electrolyte flooding through the GDE is decreased to 2.5 ± 0.6% of that with alkali cation-containing acidic electrolyte, and the FE of CO maintains above 80% over 36 h of operation at −200 mA·cm −2 .
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Journal of Energy Chemistry
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2023
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IF 13.1
Qingchun Zhang,Di Liu,Yaping Zhang,Zhiliang Guo,Minpeng Chen,Yuyun Chen,Bo Jin,Yingze Song,Hui Pan
The development of highly active, selective, and stable electrocatalysts can facilitate the effective implementation of electrocatalytic CO 2 conversion into fuels or chemicals for mitigating the energy crisis and climate problems. Therefore, it is necessary to achieve the goal through reasonable material design based on the actuality of the operational active site at the molecular scale. Inspired by the stimulating synergistic effect of coupled heteronuclear metal atoms, a novel Ni-Co atomic pairs configuration (denoted as NiN 3 ©CoN 3 -NC) active site was theoretically screened out for improving electrochemical CO 2 reduction reaction (CO 2 RR). The structure of NiN 3 ©CoN 3 -NC was finely regulated by adjusting Zn content in the precursors Zn/Co/Ni-zeolite imidazolate frameworks (Zn/Co/Ni-ZIFs) and pyrolysis temperature. The structural features of NiN 3 ©CoN 3 -NC were systematically confirmed by aberration-corrected HAADF-STEM coupled with 3D atom-overlapping Gaussian-function fitting mapping, XAFS, and XRD. The results of theoretical calculations reveal that the synergistic effect of Ni-Co atomic pairs can effectively promote the *COOH intermediate formation and thus the overall CO 2 RR kinetic was improved, and also restrained the competitive hydrogen evolution reaction. Due to the attributes of Ni-Co atomic pairs configuration, the developed NiN 3 ©CoN 3 -NC with superior catalytic activity, selectivity, and durability, with a high turnover frequency of 2265 h −1 at −1.1 V (vs . RHE) and maximum Faradaic efficiency of 97.7% for CO production. This work demonstrates the great potential of DACs as highly efficient catalysts for CO 2 RR, provides a useful strategy to design heteronuclear DACs, exploits the synergistic effect of multiple metal sites to facilitate complex CO 2 RR catalytic reactions, and inspires more efforts to develop the potential of DACs in various fields.
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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
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2023
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IF 4.4
Xiaohui Wang,Yuanxiangyi Feng,Zhe Li,Jinhua Liu,Dandan Sun,Wei Yang,Xiaowei Xing,Wenjun Liu,Hongxin Zhang
A fluorescent capillary sensor for detecting the bioanalytically and biologically relevant analytes pH, O 2 , and CO 2 has been designed. The sensor is based on single capillary tube with 2 mm inner diameter, which is simultaneous doped with emissive O 2 -sensitive indicator Ru(dpp) 3 (PF6) 2 (RuDP), pH-sensitive and CO 2 -sensitive indicator 8-hydroxypyrene-1, 3,6-trisulfonic acid trisodium salt (HPTS). The multifunctional sensor can be excited at the same wavelength and realize multi-parameter optical monitoring at the different sensing position. Studies in phosphate-buffered solutions display the excellent feasibility of the capillary sensor for fluorescence detection of pH, O 2 , and CO 2 . Overall, the multifunctional capillary sensor exhibits great potential in real-time blood gas analysis, and clinical application of multi-parameter biological detection.
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FUEL
·
2023
·
IF 7.4
Qi Huang,Zhen Zhan,Yuanting Qiao,Xueting Pan,Shaojun Xu,Bien Tan,Chunfei Wu
Covalent triazine polymers, as large π conjugated, highly porous, nitrogen riched organic semiconductors, can play a key role in tackling the fuel energy crisis and global warming issues. However, their development in photocatalytic CO 2 reduction is still rare. More effective strategies to enhance CO 2 reduction activity need to be explored. Herein, different amounts of azobenzene pendants functionalized CTPs: Azo-CTP 0 , Azo-CTP 1 , Azo-mCTP 1 and Azo-CTP 2 , were fabricated for photocatalytic CO 2 reduction with Pd loaded. Among them, Azo-mCTP 1 displayed the highest CO 2 uptake capacity up to 48.2 cm 3 g −1 (2.15 mmol g −1 ) at 273 K, and the highest CH 4 evolution rate in the water system, with selectivity highly up to 97 %. Apart from that, the azobenzene functionalization of Azo-CTP 0 could significantly boost the CO 2 reduction efficiency by 4 times. Therefore, this study provides a potentially general approach for accurately modifying organic semiconductors to enhance photocatalytic performance.
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ACS Applied Materials & Interfaces
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2021
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IF 9.229
Ningning Feng,Bingliang Wang,Zhuo Yu,Yuming Gu,Lili Xu,Jing Ma,Yonggang Wang,Yongyao Xia
Li–CO2 batteries have attracted worldwide attention because of their dual characteristics of high energy density and effective CO2 capture. However, the basic electrochemistry mechanism involved has been unclear, which is mainly confused by the complicated decomposition of organic electrolytes. Herein, water-in-salt (WIS, LiTFSI/H2O 21.0 mol/1 kg) has been explored as a suitable electrolyte for the first time to investigate the reaction mechanism of Li–CO2 batteries with different cathodes (carbon nanotube (CNT) and Mo2C/CNT, respectively). An Mo2C-based Li–CO2 battery with WIS delivers a higher energy efficiency of 83% and a superior cyclability, compared to those of the CNT-based counterpart cell. Through various ex/in situ qualitative/quantitative characterizations, the Mo2C-based Li–CO2 battery with WIS can operate on the reversible conversion of CO2-to-Li2C2O4 ((e–/CO2)ideal = 1) at lower discharge/charge overpotentials, while the CNT-based counterpart cell is based on the formation/decomposition of Li2CO3 ((e–/CO2)ideal ≈ 1.33) at high overpotentials. Such a difference in CO2 reduction products stems from the stronger interaction between Mo2C(101) and Li2C2O4 than that of the CNT and Li2C2O4 based on the density functional theory calculations, resulting in the selective stabilization of the intermediate product Li2C2O4 on the Mo2C surface.
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ACS Applied Energy Materials
·
2021
·
IF 6.024
Jing-Jing Ma,Hong-Lin Zhu,Yue-Qing Zheng,Miao Shui
Electrochemical CO2 reduction into CO with metal phthalocyanines/substrate catalysts has been receiving extensive attention due to unique activities and tunability. However, the anchoring sites and reaction mechanism still remain much debatable. In this work, through integrations of Raman spectroscopy with theoretical calculations, the anchoring location site and mechanism of CoPc on substrates were confirmed using cobalt phthalocyanine on acetylene black as model catalysts. The theoretical calculations show that the resultant CoPc/C catalyst exhibits an excellent catalytic activity for electrocatalytic CO2 reduction with low overpotential and high selectivity of CO because the defect beneath the benzene ring is more effective in anchoring CoPc.
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International Journal of Greenhouse Gas Control
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2021
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IF 3.738
Qiangwei Li,Ge Gao,Rujie Wang,Shihan Zhang,Shanlong An,Lidong Wang
Biphasic solvents are promising candidates for CO 2 capture for low regeneration energy consumption. In this study, a novel phase splitter 1-methylimidazole (1-MI) was proposed for triethylenetetramine (TETA) aqueous solvent. 1-MI was proved to act as a phase splitter to induce the phase separation and as an absorption promoter to enhance the absorption rate. By tuning the concentrations of TETA and 1-MI, good phase separation performance was obtained in TETA-1-MI biphasic solvent, achieving a CO 2 -rich phase loading of 5.41 mol/L. 13 C NMR revealed that the upper layer was the CO 2 -lean phase, containing 1-MI and a small amount of water, while the lower layer was the CO 2 -rich phase and mainly comprised of TETAH + and TETA-carbamate. The kinetics results based on the double-film theory indicated that the CO 2 absorption rate was mainly controlled by the gas film mass transfer resistance at lower CO 2 loading and then by liquid film mass transfer resistance when CO 2 loading was higher than 1 mol/L. Owing to the good phase separation behavior triggered by 1-MI, the regeneration heat of TETA-1-MI was 2.26 GJ/t CO 2 , which was comparable to that of the second-generation solvents, and 43.5 % lower than that of 5 M monoethanolamine (MEA). The present findings indicated that TETA-1-MI had a large loading capacity, high absorption rate, and low energy consumption, which can serve as a novel candidate for CO 2 capture.
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Catalysts
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2021
·Vol. 11
·期 4
·463
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IF 4.146
Zhenglong Yang,Yan Cui,Pengxiang Ge,Mindong Chen,Leilei Xu
The Ni-based catalysts have a wide range of industrial applications due to its low cost, but its activity of CO2methanation is not comparable to that of precious metal catalysts. In order to solve this problem, Ni-based mesoporous Ce0.8Zr0.2O2solid solution catalysts doped with rare earth were prepared by the incipient impregnation method and directly used as catalysts for the methanation of CO2. The catalysts were characterized systematically by X-ray powder diffraction (XRD), N2physisorption, transmission electron microscopy (TEM), energy-dispersed spectroscopy (EDS) mapping, X-ray photoelectron spectroscopy (XPS), H2temperature programmed reduction (H2-TPR), CO2temperature programmed desorption (CO2-TPD), and so on. The results show that Ni is highly dispersed in the mesoporous skeleton, forming a strong metal-skeleton interaction. Therefore, under the condition of CO2methanation, the hot sintering of metallic Ni nanoparticles can be effectively inhibited so that these mesoporous catalysts have good stability without obvious deactivation. The rare earth doping can significantly increase the surface alkalinity of catalyst and enhance the chemisorption of CO2. In addition, the rare earth elements also act as electron modifiers to help activate CO2molecules. Therefore, the rare earth doped Ni-based mesoporous Ce0.8Zr0.2O2solid solution catalysts are expected to be an efficient catalyst for the methanation of CO2at low-temperature.Keywords:Ni-based catalyst;mesoporous Ce0.8Zr0.2O2solid solution;rare earth doped;low-temperature catalytic activity;CO2methanation
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JOURNAL OF DISPERSION SCIENCE AND TECHNOLOGY
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2021
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IF 2.262
Shanshan Dai,Minmin Tao,Hongsheng Lu
CO2-responsive wormlike micelles based on ionic liquid 1,1,3,3-tetramethylguanidine-oleic acid (TMG-OA) and cationic surfactant tetradecyl trimethyl ammonium bromide (TTAB) was designed in this work, avoiding the volatileness and flammability of traditional wormlike micelles formed with amines. It provides a new method of preparing CO2-switchable wormlike micelles based on ionic liquid with acidic group. The ionic liquid TMG-OA was prepared by the direct neutralization reaction between TMG and HOA at the molar ratio of 1:1. Due to the excellent stability and switchability demonstrated by thermogravimetry (TGA) and pH, TMG-OA can be treated as nonvolatile surfactant with CO2-responsive acidic group. Then the worm-based viscoelastic fluid is formed by the electrostatic interaction between TTAB and TMG-OA, and the steady and dynamic rheology show that the viscoelastic fluid has CO2-switchable thinning behavior. The switchable behavior is consistent with the reversible transition of microstructure from wormlike micelles to emulsion, which were detected by the dynamic light scattering (DLS) and cryo-transmission electron microscope (Cryo-TEM). The microstructural transition is induced by the reversible conversation between TMG-OA component and HOA component upon CO2 and N2/heat.
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JOURNAL OF CATALYSIS
·
2021
·
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.
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RENEWABLE ENERGY
·
2021
·
IF 8.001
Naveed Ahmad,Xiaoxiao Wang,Peixu Sun,Ying Chen,Fahad Rehman,Jian Xu,Xia Xu
Electrocatalytic CO 2 reduction (ECO 2 R) is an environment-friendly way to convert CO 2 into profitable products. Amine solution recently has been employed as an electrolyte in ECO 2 R but suffers from low efficiency. Herein, aqueous solutions containing different amine-based deep eutectic solvents (DESs) were used as electrolytes for CO 2 reduction. The effect of different DESs on the CO 2 reduction was investigated at Ag, Cu, and Zn metal electrodes. Tafel and electrochemical impedance spectroscopy (EIS) were applied to understand the CO 2 reduction. DES in aqueous solution facilitates the CO 2 reduction to CO with higher faradaic efficiency of CO (FE CO ) than amine solutions and a mixture of hydrogen bond acceptor (HBA) and hydrogen bond donor (HBD). Both HBD and HBA have an influence on CO 2 reduction. [Monoethanolamine hydrochloride] [methyldiethanolamine] ([MEAHCl][MDEA]) gives high FE CO , 71% FE CO at −1.1 V vs RHE at Ag electrode, 33% higher than [MEAHCl][MEA]. Experimental results and EIS analysis reveal that the facilitation of CO 2 reduction to CO probably stems from a synergistic effect of nano-size agglomerate dispersion on Ag-surface, bicarbonate formation, exchange current density , and Cl − ions present in DESs. These findings present a feasible method to employ the aqueous MDEA-based DES solution as an electrolyte for CO 2 reduction.
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