MOLECULES
·
2024
·Vol. 29
·期 21
·4994
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IF 4.2
Fan Ma,Hong-Wei Lin,Zizi Li,Wen-Jing Li,Jia-Wei Wang,Gangfeng Ouyang
Noble-metal-free CO2reduction systems based on cobalt phthalocyanine (CoPc) and its derivatives have demonstrated remarkable photocatalytic performances; however, their structure-activity relationship with electronic tuning remains unexplored. Herein, we now provide a systematic study to investigate the electron effects of substituents on theCoPcfamily in photocatalytic CO2reduction, where a Cu(I) heteroleptic photosensitizer is utilized. The highest performance can be achieved using cobalt tetracarboxylphthalocyanine in light-driven CO2-to-CO reduction, with a maximum turnover number of 2950 at 450 nm and an outstanding apparent quantum yield of 63.5% at 425 nm, over ten times the activity with the tetra-dimethylamino-substitutedCoPcderivative. The favorable electron-withdrawing effects have been further verified by DFT calculations and cyclic voltammetry, which reduces the overpotential required for CO2reduction and decreases the Gibbs free energy of the catalyst active intermediates, particularly the CO-desorption energetics.
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JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2025
·
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.
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Surfaces and Interfaces
·
2024
·
IF 5.7
Pengfei Zhu,Mengrong Geng,Shuang Qin,Heyang Cao,Zhenhong He,Xinhua Gao,Chuanyi Wang
The conversion of CO 2 into chemical products or fuels of great value always remains an outstanding challenge. Here, we report a heterojunction Fe@C/Ni 2 P composite catalyst obtained by preparing MIL-100(Fe) derived Fe@C confined Ni 2 P nanoparticles, which is applied to photothermal catalytic CO 2 hydrogenation with H 2 O. Without adding any sacrificial agents or co-catalysts, the optimal Fe@C/Ni 2 P sample shows higher yields for CO 2 -to-C 2 H 6 and CO 2 -to-CO yield of 5.83 μmol g −1 h −1 and 179.9 μmol g −1 h −1 than that of pristine Fe@C and Ni 2 P, respectively. The experimental results indicated that the obtained Fe@C/Ni 2 P can act as catalytic sites to adsorb, activate, and convert CO 2 under low-intensity LED light irradiation (420 nm) with a temperature of 200 ℃. The physical structure, photochemical properties and energy band structure of the Fe@C/Ni 2 P composite catalysts were investigated by XRD, XPS, FT-IR, TEM, BET, respectively. Furthermore, the reaction pathway of Fe@C/Ni 2 P photothermal catalytic CO 2 hydrogenation with H 2 O to C2 products and CO were systematically analyzed by in situ infrared spectroscopy (DRIFTS).
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FUEL
·
2024
·
IF 6.7
Yurou Shao,Yangyang Jiang,Dong Wang,Benshuai Guo,Jingyan Zhao,Zhibin Zhou,Jianqiu Chen,Ruixin Guo,Yuntao Lei,Lili Jin
Capturing and recovering carbon dioxide (CO 2 ) from the combustion of fossil fuels is an effective way to reduce carbon emissions, as CO 2 is not only a threat to the environment but also an important C1 feedstock. In the current work, a series of trioctylphosphine oxide (TOPO)-based azole deep eutectic solvents (DESs) have been synthesized for the efficient absorption of CO 2 . The solid–liquid phase diagrams of the DESs were projected using the prediction data from COSMO-RS, and the experimental melting temperature was found to be lower than that of the prediction. These DESs exhibit satisfactory physical properties, including low viscosities (20–60 mPa·s) and high thermal decomposition temperatures (up to 192.5 °C). Furthermore, the CO 2 uptake process was carried out at 35 °C and 0.1 MPa, and the results demonstrated that the CO 2 uptake capacity was positively influenced by hydrogen bond donors (HBDs), mole fraction of HBDs, temperatures, and humidity. Among the DESs, TOPO-imidazole (1:1) was notable for its high absorption capacity of 0.062 mol CO 2 /mol DES, as well as its excellent recyclability. There was no discernible decline in the CO 2 uptake capacity after four absorption–desorption cycles. In this work, NMR and FT-IR investigations indicated the physical absorption mechanism of this system. The designed DESs have the potential to be effective absorbents for efficient reversible CO 2 capture.
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JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
·
IF 9.4
Yifei Ye,Yuanyuan Cui,Li Yang,Jiaxu Zhang,Jianmin Sun
A novel external-skeleton B-containing ionic liquid modified SBA-15 catalyst BBN-Imi-SBA-15-I (BBN denotes borabicyclo[3.3.1]nonane, Imi represents imidazolium ionic liquid) was successfully constructed by a post-modification method for efficiently catalyzing CO 2 -epoxide coupling reaction under both metal- and solvent-free conditions. 5BBN-Imi-SBA-15-I (5 refers to the molar ratio of Si to B), thanks to its synergistic effects of Lewis acid, weak base sites from tertiary amine and quaternary ammonium, hydrogen bond group and nucleophilic group, displayed good catalytic activity with 97 % product yield and 99 % selectivity at 100 °C, 2 MPa in the absence of cocatalyst. The obtained catalyst demonstrated good recyclability during six consecutive catalytic runs, also presented generality for various mono-substitute epoxides. Through in-situ NH 3 diffuse reflectance infrared Fourier transform spectroscopy (NH 3 -DRIFTS) characterization, the Lewis acidity of organo-boron was verified. Besides, kinetics research also proved the positive effect of multiple active components on efficient catalysis under milder conditions over SiO 2 -based metal-free catalysts.
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Catalysis Science & Technology
·
2024
·
IF 4.4
Huangdong Wang,Zhihua Guo,Heng Zhang,Lin Jia,Min Sun,Lifeng Han,Haorun Li,Yan Guo,Shanghong Zeng
Arranging the active ingredients on the support surface at the molecular or atomic scale to create high-selectivity sites for the electrocatalytic CO2 reduction reaction (CO2RR) holds great promise, which is highly challenging. In this study, we report a strategy for constructing a bimetallic Ag–Ni electrocatalyst with Ni nanoparticles for H2O dissociation, as well as Ni atoms in the carbon skeleton and Ag nanoparticles on the surface for the CO2RR. These sites synergistically enable high selectivity for improving the conversion of CO2 to CO. Specifically, the FECO reaches 99.3% on Ag–Ni/CB at −0.8 V vs. RHE, and its FECO can be maintained over 95.8% in the potential range from −0.8 to −1.1 V vs. RHE. Our research presents an approach for alignment of bifunctional two-component active sites on the surface of a carbon support.
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ACS Applied Polymer Materials
·
2025
·
IF 4.7
Yanling Liu,Xiao Peng,Yuan Li,Fei Wang,Xue Ai,Yuxi Huang,Xin Sun,Jie Zhao,Kai Li
Membrane separation technology has garnered significant attention for CO2 separation and purification, with mixed matrix membranes (MMMs) emerging as promising candidates due to their advantages of ease of processing, high mechanical strength, and thermal stability. The development of effective fillers for separation performance becomes one of the key foci in this area. In this work, CC3, a type of porous organic cages (POCs), was synthesized and functionalized with two amino-containing materials of different chain lengths. Polyethylenimine (PEI) and diethylenetriamine were used as modification agents to successfully graft amino groups onto the CC3 crystals to form defect-free Pebax mixed matrix membranes containing amino-functionalized CC3. The special porous structure of CC3 increases the gas permeability of the mixed matrix membrane by providing extra channels for the transportation of CO2. Besides, amino groups on functionalized CC3 interact with the chains of Pebax through hydrogen bonding, thus improving the compatibility between filler and matrix. The amino groups can further facilitate the transport of gases across the membrane through reversible reactions with CO2, which is further enhanced under humid conditions. Under optimal conditions, at 1 bar and 30 °C, the CO2 permeability of Pebax/PEI@CC3-MMMs was 342.33 Barrer with a selectivity of 33.38, while Pebax/DETA@CC3-MMMs exhibited a CO2 permeability of 273.34 Barrer and a selectivity of 35.77. This work demonstrates that amino-functionalized POCs (CC3) can effectively enhance the CO2 permeability and the CO2/N2 selectivity, which may provide a way to develop high-performance mixed matrix membranes with superior separation properties.
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SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Xinpeng Guo,Jian Yin,Haishuai Cui,Jiating Gong,Siqi Cheng,Yunlong Li,Xinglu Deng,Feiying Tang,Shaofeng Xiong,Pingle Liu
The N-formylation reaction of amines by CO 2 hydrogenation is a promising method for converting CO 2 into chemical products with industrial application value. However, most of the currently developed catalysts are metal-homogeneous catalysts, which contain metal pollution and are not easy to recycle. Thus, we modified carbon nanotubes with N-containing amino compounds and prepared a polyethylenimine (PEI) grafted carbon nanotubes metal-free catalyst, which was applied to the N-formylation reaction of CO 2 and aniline. By adjusting the grafting concentration and the type of amino compound, the acid-base properties and surface defects of the catalyst were regulated. The CNT-0.5PEI catalyst had the optimal catalytic activity after 12 h of reaction at 80 °C, with a conversion rate of 95.41 % for aniline and a selectivity of 94.04 % for the target product N-formylaniline. It reveals that its catalytic performance can be comparable to the reported homogeneous catalysts. Our research found that increasing the surface defects and basic sites of carbon nanotubes was conducive to the enrichment and activation of CO 2 , thereby enhancing the catalytic activity. The experimental and calculation results indicate that the reaction has relatively low activation energy under the catalysis of CNT-0.5PEI, and the catalyst has the strongest adsorption capacity for CO 2 and aniline reactants. In addition, the CNT-0.5PEI displays a wide range of substrate applicability and excellent cyclic stability. Therefore, cheap and environmentally friendly metal-free modified carbon nanotube catalyst is an ideal substitute for scarce and polluting metal homogeneous materials. It has important reference significance for the efficient conversion and utilization of CO 2 catalyzed by metal-free catalyst.
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Journal of CO2 Utilization
·
2024
·
IF 7.2
Zhenrong Zheng,Junjie Dong,Jian Wang,Hongyang Wang
The majority of conventional flame retardants are made by chemical processes using petroleum resources, which cause serious pollution and waste of resources in the ecological environment. In this paper, flame retardants such as L-aspartic acid, DL-serine, L-tyrosine, L-lysine, L-phenylalanine, L-histidine, L-tryptophan, and glycine were employed to finish poly-(ethylene terephthalate) (PET) fabrics with supercritical CO 2 fluid. Scanning electron microscope (SEM) and Energy dispersive spectroscopy (EDS) were used to examine. the microstructure and chemical composition of flame-retardant PET fabrics. The limiting oxygen index (LOI) test and the vertical combustion test were used to assess the flame-retardant qualities of PET fabrics. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to test and assess the thermal properties of PET fabrics. The strength test was used to assess the mechanical properties of PET fabrics. The results showed that the amino acid flame retardants were successfully finished on the PET fabrics by supercritical CO 2 (SC-CO 2 ) technology and improved the thermal stability of the PET fabric. In comparison to untreated PET fabric, the elongation at break was 13–15 % greater, and the breaking strength was not reduced. Among them, the PET fabrics treated with L-aspartic acid and L-lysine had better flame-retardant performance, there were no droplets, the LOI values were greater than 30 %, and the char length was less than 10 cm. After 45 minutes of soaping and 3 times of washing, the LOI values were still above 28 %, and there were no droplets. Therefore, the PET fibers treated with amino acids using SC-CO 2 technology effectively improved the flame-retardant performance of PET fabrics.
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Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
Yang Kang,Li Ming,Gao Tianqi,Xu Guoliang,Li Di,Zheng Yao,Li Qiang,Duan Jingjing
Industrial CO 2 electrolysis via electrochemical CO 2 reduction has achieved progress in alkaline solutions, while the same reaction in acidic solution remains challenging because of severe hydrogen evolution side reactions, acid corrosion, and low target product selectivity. Herein, an industrial acidic CO 2 electrolysis to pure HCOOH system is realized in a proton-exchange-membrane electrolyzer using an acid-tolerant Bi-based metal-organic framework guided by a Pourbaix diagram. Significantly, the Faradaic efficiency of HCOOH synthesis reaches 95.10% at a large current density of 400 mA/cm 2 with a high CO 2 single-pass conversion efficiency of 64.91%. Moreover, the proton-exchange-membrane device also achieves an industrial-level current density of 250 mA/cm 2 under a relatively low voltage of 3.5 V for up to 100 h with a Faradaic efficiency of 93.5% for HCOOH production, which corresponds to an energy consumption of 200.65 kWh/kmol, production rate of 12.1 mmol/m 2 /s, and an energy conversion efficiency of 38.2%. These results will greatly aid the contemporary research moving toward commercial implementation and success of CO 2 electrolysis technology.
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Journal of Energy Chemistry
·
2024
·
IF 14
Zhijie Zhang,Xuesheng Wang,Junyi Qian,Jiayue Xu
Heterojunction construction, especially S-scheme heterojunction, represents an efficient universal strategy to achieve high-performance photocatalytic materials. For further performance stimulation of these well-designed heterojunctions, modulating the interfacial internal electric field (IEF) to steer dynamic charge transfer represents a promising approach. Herein, we realized the precise regulation of Fermi level ( E F ) of the oxidation semiconductor (mesoporous WO 3− x ) by tailoring the concentration of oxygen vacancies (V O ), maximizing the IEF intensity in Cs 2 CuBr 4 @WO 3− x (CCB@WO 3− x ) S-scheme heterojunction. The augmented IEF affords a robust driving force for directional electron delivery, leading to boosted charge separation. Hence, the developed CCB@WO 3− x S-scheme heterojunction demonstrated outstanding photocatalytic CO 2 reduction performance, with the electron consumption rate ( R electron ) up to 390.34 μmol g −1 h −1 , which is 3.28 folds higher than that of pure CCB. An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations, electron spin resonance (ESR), photo-irradiated Kelvin probe force microscopy (KPFM), and in-situ X-ray photoelectron spectroscopy (XPS). Finally, the CO 2 photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and DFT theoretical calculations.
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ACS Applied Materials & Interfaces
·
2024
·
IF 8.3
Ting Niu,Yulu Mao,Yujing Lv,Mengjie Li,Yongchun Liu,Peng Yang,Quan Gu
Modification of g-C3N4 with metal-free biomaterials through an environmentally friendly, low-energy, facile, and rapid single-step method is desired for the preparation of photocatalysts with efficient activity and high selectivity of CO2 reduction but remains a great challenge. Herein, we develop a phase-transitioned protein modification strategy for photocatalysts through superfast amyloid-like protein assembly on surfaces using a one-step sequential coating method. Metal-free carbon nitride/protein heterojunction composite photocatalysts (the phase-transitioned lysozyme (PTL), phase-transitioned bovine serum albumin (PTB), and phase-transitioned ovalbumin (PTO)-coated carbon nitride@SiO2 (CN@SiO2) and bioinspired carbon nitride hollow nanospheres (CN-HS) obtained by etching of CN@SiO2) are prepared using lysozyme, bovine serum albumin, and ovalbumin. The insulator–semiconductor heterojunctions formed at the protein–carbon nitride interface promote the migration and separation of photogenerated charges. The exposed hydrophobic alkyl and aryl groups of the surface-modified protein enable the formation of a CO2–aqueous solution–photocatalyst three-phase interface on the catalyst surface and the exposed −NH2 groups provide sites for CO2 adsorption, which effectively increases CO2 mass transfer and its adsorption as well as hydrophobicity, promoting CO2 reduction and inhibiting hydrogen production. Therefore, protein modification effectively improves the CO2 reduction activity and CO selectivity. For instance, compared to CN-HS, the CO yield of the PTL-modified CN-HS (1346.5 μmol g–1) increased by 24.5 times and the CO selectivity reached 90.5%. These findings represent a critical advancement in the surface modification of carbon nitride for CO2 reduction and the design of bioinspired materials for various applications.
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