ACS Applied Materials & Interfaces
·
2023
·
IF 9.5
Yuying Zhao,Qixin Yuan,Kang Sun,Ao Wang,Ruting Xu,Jing Xu,Yan Wang,Mengmeng Fan,Jianchun Jiang
Carbon material is considered a promising electrocatalyst for the CO2 reduction reaction (CO2RR); especially, N-doped carbon material shows high CO Faradic efficiency (FECO) when using pyridinic N species as the active site. However, in the past decade, more efforts were focused on the preparation of various carbon nanostructures containing abundant pyridinic N species and few researchers studied the electronic structure modulation of the pyridinic N site. The curvature of the carbon substrate is an easily controllable parameter for modulating the local electronic environment of catalytic sites. In this research, carbon nanotubes (CNTs) with different diameters are applied to modulate the electronic environment of pyridinic N by the curvature effect. The pyridinic N sites doped on CNTs with the average curvature of 0.04 show almost 100% FECO at the current density of 3 mA cm–2 at −0.6 V vs RHE and 91% FECO retention after 12 h test, which is superior to most of the carbon-based electrocatalysts. As demonstrated by density functional theory simulation, the pyridinic N site forms a strong local electric field around the nearby C active site and protrudes out of the curved CNT surface like a tip, which remarkably enriches the protons around the adsorbed CO2 molecule.
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高影响因子
ENERGY
·
2023
·
IF 9
Xin Yin,Shufeng Shen
Water-lean amine absorbents have potential in reducing regeneration energy consumption for post-combustion CO 2 capture. In this work, dimethyl sulfoxide (DMSO) was proposed as a cosolvent to develop water-lean monophasic absorbents for capturing CO 2 in the simulated flue gas treatment. CO 2 absorption and desorption performance has been investigated for nonaqueous/water-lean systems involving three secondary alkanolamines and compared with the conventional monoethanolamine (MEA). Effect of water content in these absorbents on reaction products, regeneration energy consumption and capture performance was also discussed. Interestingly, the DMSO-based amine blends can maintain the monophasic state before and after CO 2 absorption at the investigated conditions. Water-lean absorbent of 2-(butylamino)ethanol (BAE)/DMSO/H 2 O was proposed for energy-efficient CO 2 capture, due to the observed high cyclic capacity and super-low energy consumption. Increasing water content in the absorbents can slightly improve the absorption capacity and cyclic capacity, but significantly increased the regeneration energy. Maintaining the water content not higher than 10 mass% can reduce the regeneration energy by 48–55% compared with the benchmark aqueous 30% MEA (4.05 MJ kg −1 CO 2 ), which makes the proposed absorbent as a compelling candidate in the conventional CO 2 capture process without major process modification.
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CARBON
·
2023
·
IF 10.9
Qiuchan Li,Lang He,Yubin Zeng,Yan Zhao,Mingyue Ding
Obtaining highly active and selective target products is both promising and challenging, and can be achieved by regulating the adsorption and desorption energy of reaction intermediates, as well as the transfer of electrons under visible light. Herein, an efficient CNGA/CdS photocatalyst based on ultrathin porous nitrogen vacancies carbon nitride (CNGA) nanosheets (thickness <1 nm) with CdS nanoparticles was synthesized by a facile route for visible-light photocatalytic CO 2 reduction. As a result, the rate of CO production was 32.75 μmol g −1 h −1 , which was 17.24 and 32.75 times that of CN and CdS under visible light (λ ≥ 420 nm) without sacrificial agents and cocatalysts . Importantly, introducing CdS nanoparticles into CNGA could improve the selectivity of CO 2 to CO by nearly 100% (yield-based selectivity). Finally, the photocatalytic mechanism was explored by in-situ FTIR spectra and DFT calculations, and the results presented that the formation of heterostructures facilitated the generated *CO groups to modulate the reaction pathway of photocatalytic CO 2 reduction. This work is expected provide a reference for the design of photocatalysts for photoreduction CO 2 with accurate products under visible light.
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Small
·
2023
·Vol. 19
·期 45
·2303405
·
IF 13.3
Mengping Liu,Ganbing Zhang,Ruiqi Ming,Xin Fu,Ruiyi Jiang,Lihong Tian,Xiaobo Chen
Defects on metal oxide have attracted extensive attention in photo-/electrocatalytic CO 2 reduction. Herein, porous MgO nanosheets with abundant oxygen vacancies (V o s) and three-coordinated oxygen atoms (O 3c ) at corners are reported, which reconstruct into defective MgCO 3 ·3H 2 O exposing rich surface unsaturated -OH groups and vacancies to initiate photocatalytic CO 2 reduction to CO and CH 4 . In consecutive 7-cycle tests (each run for 6 h) in pure water, CO 2 conversion keeps stable. The total production of CH 4 and CO attains ≈367 µmol g cata −1 h −1 . The selectivity of CH 4 gradually increases from ≈3.1% (1 st run) to ≈24.5% (4 th run) and then remains unchanged under UV-light irradiation. With triethanolamine (3.3 vol.%) as the sacrificial agent, the total production of CO and CH 4 production rapidly increases to ≈28 000 µmol g cata −1 in 2 h reaction. Photoluminescence spectra reveal that V o s induces the formation of donor bands to promote charge carrier seperation. A series of trace spectra and theoretical analysis indicate Mg-V o sites in the derived MgCO 3 ·3H 2 O are active centers, which play a crucial role in modulating CO 2 adsorption and triggering photoreduction reactions. These intriguing results on defective alkaline earth oxides as potential photocatalysts in CO 2 conversion may spur some exciting and novel findings in this field.
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CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Yuke Zhang,Yi Huang,Shangqing Chen,Lijuan Shi,Jiancheng Wang,Qun Yi,Feng Pei
The high-efficiency capture of CO 2 from biogas by adsorption is highly desirable, which, yet faces the challenges regards of the unsatisfactory adsorption efficiency, selectivity, and regeneration performance. Herein, ionic ultramicroporous metal organic frameworks (IUM-MOFs) with high CO 2 affinity are constructed by one-step in-situ coordination strategy and used for CO 2 /CH 4 separation. The phenoxylate anion-functionalized ionic liquid (FIL) serves as competitive ligands in the formation of IUM-MOFs. The oxyl group exhibits high affinity with CO 2 as the Lewis basic center, while the rigid counterion occupies the adsorption space of CH 4 in the cavities of IUM-MOFs, thus bringing about superior CO 2 adsorption capacity of 149 cm 3 g −1 (150% higher than that of Cu-BTC) and high IAST predicted selectivity with CH 4 of 22 under atmospheric condition. Mechanism analysis demonstrated that the formation of hydrogen bonds between CO 2 with coordinated IL and H 2 O and IL-enhanced polarity of MOFs benefit to the CO 2 adsorption. In addition, the IUM-MOFs could be facilely regenerated at 120 °C with favorable recycling stability. This work provides facile strategy for the rational design of IUM-MOFs and lays useful insights for structural tuning to promote their applications.
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Small
·
2023
·Vol. 19
·期 49
·2304084
·
IF 13.3
Xiaolei Wang,Wenqian Wang,Bowen Liu,Zichen Song,Zhiyu Ren,Honggang Fu
Although the electron-withdrawing effect of gold (Au) is highlighted in catalytic reactions, its enhancement mechanism for electron transport, especially in the electrochemical process, is still unclear. Herein, Au-decorated Bi 2 O 3 (Au-Bi 2 O 3 ) is proposed as a proof-of-concept to investigate the electron-withdrawing effect in the electrocatalytic CO 2 reduction reaction (eCO 2 RR) process. Evidence from in situ Raman spectra and in situ XRD tests reveals that, compared to Bi 2 O 3 , Bi species in Au-Bi 2 O 3 can be reduced to metallic Bi more rapidly and more easily driven by the electron-withdrawing effect of Au. The XPS tests after eCO 2 RR further validates the transformation from Bi 3+ to Bi 0 in Au-Bi 2 O 3 is more complete. Meanwhile, in the in situ Fourier transform infrared (FTIR) spectra, the key intermediates (CO 2 * − and OCHO* − ) appear at the more positive potential, indicating that metallic Bi is favorable for eCO 2 RR due to the lower energy barrier as corroborated by density function theory (DFT) calculations. Au don't directly participate in the conversion from CO 2 to formate as the reaction sites, but utilize the electron-withdrawing effect to motivate Bi-sites to deliver higher catalytic activity and higher selectivity to formate at a lower applied potential. This study not only has an insight into the electron-withdrawing effect of Au on the eCO 2 RR process, but also develops a new perspective for engineering electron-withdrawing effect in electrocatalysts for high-efficient CO 2 -to-formate conversion.
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APPLIED CATALYSIS A-GENERAL
·
2023
·
IF 5.5
Taoning Lei,Qi Dang,Tong Wu,Yun Wu,Jingyi Yu
Electrochemical reduction of CO 2 enables a flexible and efficient way of converting CO 2 into diverse products. Cu 2 O is regarded as a crucial species for electrocatalytically transforming CO 2 to methanol while facing challenges such as the deactivation of the catalyst and low selectivity of desired products. Therefore, the modification of Cu 2 O and the improvement of its catalytic activity needs to be addressed. Herein, we reported a novel synthesis of Cu 2 O nanocubes (Cu 2 O-cube) using the wet chemical method and demonstrated a Faradaic efficiency of 29.1 % for methanol. We found Cu 2 O (100) facet was responsible and beneficial to improve methanol production . The performance degradation at different potentials due to the deactivation of Cu 2 O-cube were revealed from the changes of surface morphologies by scanning electron microscope (SEM). The electrocatalytic activity of Cu 2 O-cube was further enhanced by embedding Cu 2 O-cube into ZnO nanowires (ZnO@Cu 2 O-cube) through drop-drying, leading to a Faradaic efficiency of 38.9 % towards methanol at − 0.45 V vs. RHE. For parallel comparison, an alternative binding form of ZnO and Cu 2 O was investigated through stacking Cu 2 O film onto ZnO nanowires (ZnO@Cu 2 O-film) through electrodeposition . The results elucidated that the existence of ZnO tended to suppress the production of ethanol and the binding site of ZnO-Cu 2 O could improve the selectivity of methanol.
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2023
·
IF 5.2
Lipei Fu,Ziran Zhang,Xinxin Qiu,Yufei Zheng,Minglu Shao,Yingrui Bai,Zhangkun Ren,Wenzhe Si,Jiafeng Jin,Yanyu Xu,Kaili Liao
A novel rapidly switchable CO 2 /N 2 -responsive Pickering emulsifier based on supramolecular amphiphilic surfactants (SDOA) and nano-SiO 2 has been fabricated. SDOA was constructed by mixing Jeffamine D-230 and oleic acid (HOA) at 1:1 stoichiometric ratio. Compared with conventional small-molecule emulsifiers, the novel rapidly switchable CO 2 /N 2 -responsive Pickering emulsifier was prepared with inexpensive raw materials by a simple method, and there was no contaminant generation during synthesis. A new CO 2 /N 2 -responsive Pickering emulsion was prepared on this basis, and its stable performance and responsiveness were investigated in depth. The results show that this emulsion can be stable for a long time (more than 30 days) at a low surfactant dosage (0.5 mmol/L) through in situ hydrophobization of SiO 2 nanoparticles by hydrogen bonding and electrostatic adsorption. In addition, the emulsion broke rapidly and completely after 10 s of CO 2 introduction into the stable emulsion, and the emulsion could be reconstructed in response to N 2 purging for 5 min at 60 ℃ followed by homogenization . The switching behavior of the emulsion is due to decomposition of the pseudo amphiphile by bubbling CO 2 into the system and both the protonated D-230 ions and the neutral HOA produced have no in situ hydrophobization to SiO 2 particles. At 60 ℃, the influx of N 2 will drive out CO 2 , making HOA re-transform into hydroxide ion, and after re-combining with D-230 ion, it can again perform in-situ hydrophobization on SiO 2 particles, thus forming a stable emulsion. Thanks to the ability of SiO 2 nanoparticles and D-230 ions to maintain electrostatic adsorption after the passage of CO 2 , compared with previous studies, the emulsion can be completely demulsified at a higher pH value (about 5.5), fewer bicarcarbonate roots are formed, less CO 2 needs to be introduced, and N 2 required to re-stabilize the emulsion is also reduced. This greatly increases the response efficiency of the emulsion and reduces the energy loss and the cost of putting the emulsion system into practical application. This research has important implications for fossil fuel generation, production and transportation of crude oil, and other areas.
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Small
·
2023
·Vol. 19
·期 45
·2302022
·
IF 13.3
Hai-Bing Zhao,Jia-Nan Huang,Qi Qin,Hong-Yan Chen,Dai-Bin Kuang
Rational design and facile synthesis of efficient environmentally friendly all-inorganic lead-free halide perovskite catalysts are of great significance in photocatalytic CO 2 reduction. Aiming at photogenerated charge carrier separation and CO 2 reaction dynamics, in this paper, a CsCuCl 3 /Cu nanocrystals (NCs) heterojunction catalyst is designed and synthesized via a simple acid-etching solution process by using Cu 2 O as the sacrificed template. Due to the disproportionation reaction of Cu 2 O induced by concentrated hydrochloric acid, Cu NCs can be deposited onto the surface of CsCuCl 3 microcrystals directly and tightly. As revealed by photoelectrochemical analysis, in situ Fourier transform infrared spectra, etc., the Cu NCs contribute a lot to extracting photoelectrons of CsCuCl 3 to improve the charge separation efficiency, regulating the CO 2 adsorption and activation, and also stabilizing the reaction intermediates. Therefore, CsCuCl 3 /Cu heterojunction exhibits a total electron consumption rate of 58.77 µmol g −1 h −1 , which is 2.9-fold of that of single CsCuCl 3 . Moreover, high CH 4 selectivity of up to 92.7% is achieved, which is much higher than that of CsCuCl 3 (50.4%) and most lead-free halide perovskite-based catalysts. This work provides an ingenious but simple strategy to rationally design cocatalysts in situ decorated perovskite catalysts for manipulating both the catalytic activity and the product selectivity.
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CHEMICAL ENGINEERING SCIENCE
·
2023
·
IF 4.7
Wenji Zheng,Ziheng Li,Yan Dai,Xiangcun Li,Xuehua Ruan,Xiaobin Jiang,Xiujuan Zhang,Gaohong He
The regulation on cage size and CO 2 -philic environment of metal–organic frameworks (MOFs) is essential to improve CO 2 capture. In this work, [Bmim][Tf 2 N] was proposed to position into cages of ZIF-8 to achieve the selective permeation of CO 2 by pore screening and CO 2 adsorption. [Bmim][Tf 2 N] was introduced into cages of ZIF-8 by “adsorption-infiltration” strategy. Due to the strong interaction between [Tf 2 N] − and ZIF-8, the cages present a CO 2 -philic environment, which preferentially attracts CO 2 to enter these cages, ensuring the dissolution selectivity of CO 2 . Besides, the proper cage size tuned by [Bmim][Tf 2 N] provides CO 2 with a faster transport channel due to its smaller average kinetic diameter than N 2 , guaranteeing the diffusion selectivity of CO 2 . Consequently, the CO 2 separation in [Bmim][Tf 2 N]@ZIF-8/Pebax MMMs is intensified. With increasing the [Bmim][Tf 2 N] content in cages of ZIF-8, the pore volume by BET results decreases and the CO 2 adsorption from molecular simulation increases. In response, the CO 2 /N 2 selectivity of [Bmim][Tf 2 N]@ZIF-8/Pebax MMMs is enhanced constantly. Meanwhile, the CO 2 permeability is declined due to the narrowed cage size. All of these results demonstrate the significance of pore screening and CO 2 adsorption induced by [Bmim][Tf 2 N]. Specifically, [Bmim][Tf 2 N] 8 @ZIF-8/Pebax MMM at filler loading of 15 wt% exhibits the CO 2 permeability of 108.3 Barrer and the CO 2 /N 2 selectivity of 86.7, exceeding the 2008 Robeson upper bound. Especially the CO 2 /N 2 selectivity locates at a higher level than those of most reported works, indicating that appropriate tuning of the physicochemical properties within the nanocages of MOFs is significative to improve CO 2 capture.
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JOURNAL OF POLYMER RESEARCH
·
2022
·Vol. 29
·期 11
·1-12
·
IF 3.061
He Zonglin,Xian Wenqi,Ding Zhu,Wang Chaozhi,Huang Zhenhong,Song Lina,Liu Baohua
Propylene carbonate diols (PCD) were synthesized from propylene carbonate and ethylenediamine (EDA), iso-phorone diamine (IPDA) and diethylenetriamine (DETA), respectively. The obtained PCDs were used as extenders to prepare the waterborne polyurethane (WPU). The properties of PCD based WPUs were compared to the that of WPU used butane-1,4-diol (BDO) as extender. The structures of PCDs were characterized by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR). The yields, melting points and viscosity of PCDs were tested. The mechanical properties, water absorption, water contact angle, adhesion, pencil hardness, thermal gravimetric analysis (TGA), differential scanning calorimeter (DSC) and dynamic mechanical analysis (DMA) of WPU films were also characterized. The results showed that PCDs with urethane bond in the structure were successfully synthesized and the yields were approximately 99% after 3 h of reaction. Compared to the WPU used BDO as extender, WPU films derived from PCDs exhibited superior tensile strength, outstanding adhesion and pencil hardness, lower water contact angle and water absorption, and higher initial thermal decomposition temperature.
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INORGANIC CHEMISTRY
·
2022
·
IF 5.436
Amir Said,Caiyun Liu,Chang Gao,Dexin Wang,Huihui Niu,Yanshu Liu,Guo Wang,Chen-Ho Tung,Yifeng Wang
The CO2 cycloaddition to epoxides is an efficient method for CO2 capture and storage, important not only for reducing greenhouse gas emission but also for producing cyclic carbonates, which are valuable industrial materials. In this study, we report a novel high-nuclearity titanium oxide cluster (TOC) inlayed with main-group element Pb2+, H2Ti16Pb9O24(SA)18(DMF)10(OH2)2 (denoted as 1; SA = salicylate; DMF = N,N-dimethylformamide), which has the property of visible-light absorption and has shown high catalytic activities for cycloadditions of CO2 under visible-light irradiation. The cluster was synthesized in a high yield in a facial solvothermal process. Its structure and electronic structure were characterized by single-crystal X-ray diffraction, density functional theory calculations, and complementary techniques. The cycloaddition reactions were performed under solvent-free conditions. While the catalytic activity due to the Lewis acidity was moderate, visible-light irradiation further folded the reaction rates. The turnover number reached 3400 with a turnover frequency of 120 h–1. Mechanism studies indicated a synergistic effect of the Lewis acidity and photogenerated charge carriers. The performance of 1 in reversible I2 uptake was also investigated. This study demonstrates the high potential of heterometal-decorated TOCs in the cost-effective and efficient CO2 cycloaddition reaction under mild conditions.
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危险品化学品经营许可证（带存储）