Chem Catalysis
·
2023
·
IF 9.4
Guiru Zhang,Ke Ye,Baoxin Ni,Kun Jiang
Using renewable electricity to electrochemically convert CO 2 into value-added chemicals and fuels is a promising way to curb anthropogenic carbon emissions. In past years, exciting achievements have been witnessed on the robust and selective electrochemical CO 2 reduction reaction, via either the delicate design of electrocatalytic materials or the local reaction environment engineering toward a practical system integration. In this perspective, we overview recent advances of extrinsic reaction environment effects in promoting CO 2 -to-C 2+ conversion from three spatial aspects: (1) the chemical and physical surface modification, (2) the electrolyte composition and adjoint concentration gradient for both cations and anions, and (3) the mass transport regulation. Prevailing hypotheses, together with experimental and/or theoretical progress, have been critically assessed along with a deepened mechanism understanding of those extrinsic tuning knobs. Finally, challenges and future opportunities for more efficient C 2+ production are provided in terms of fundamental interface engineering and technical electrolyzer implementation.
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2023
·
IF 8.4
Jiaqi Ruan,Yichao Tong,Jingyu Ran,Changlei Qin
A large amount of spent lithium batteries, especially lithium iron phosphate (LiFePO4), is discarded due to their limited lifespan and poses a great threat to the environment. At the same time, the potential application of Li4SiO4, an efficient high-temperature CO2 sorbent, is largely limited by the high cost of lithium resources. Thus, the preparation of Li4SiO4 from spent LiFePO4 batteries has great potential for achieving waste recycling and reducing CO2 capture costs. However, the process of recycling spent LiFePO4 batteries to synthesize Li4SiO4 sorbents still needs to be well investigated. This work proposes to simplify the preparation scheme by combing precipitation, Na doping, and synthesis processes and further optimizing the key variables of pH, Na2CO3 ratio, and heating rate. An optimal condition is determined to be pH = 9, Na2CO3 ratio = 11 wt %, and heating rate = 5 °C/min, and the sorbent prepared shows a superior stable CO2 capacity of 0.24 g/g in 80 adsorption/desorption cycles. The work develops an effective Li4SiO4 preparation scheme from spent LiFePO4 batteries with largely enhanced CO2 adsorption performance and reduced cost and could achieve a win–win situation in waste recycling and CO2 mitigation.
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR STRUCTURE
·
2023
·
IF 3.8
Kaixuan Shen,Han Zhao,Yihao Zhao,Xiaoxiang Wang,Ping Cheng,Congfei Yao,Jie Zhang,Yongpeng Yang,Weijia Huang
With regard to the physical absorbents for CO 2 removal, the alteration of carbon-chain structure may benefit the CO 2 absorption performance. However, the relationship between the carbon-chain structure of ketones absorbents and their CO 2 absorption capacity has rarely been studied, and the related mechanism is unclear. In this study, theoretical calculations and thermodynamic experiments were carried out to explore the effects of the carbon-chain length and isomerism of ketones on their CO 2 absorption performance. The density functional theory (DFT) simulations show that the F-∥ configuration is more stable than the others for the CO 2 +ketone complex in most cases. The followings are obtained according to the experimental results, which are pretty consistent with DFT calculations. The dissolution of CO 2 in the ketone is a typical physical process. As the number of carbon atom increases, the CO 2 absorption capacity of straight-chain ketones increases. Straight-chain ketones exhibit higher CO 2 absorption capacity than branched-chain ones. The effect of increasing carbon-chain length and isomerism on CO 2 absorption capacity are both stronger for the ketones with fewer carbon atoms; the influence mechanism can be attributed to different degrees of weak hydrogen-bond interaction between CO 2 and ketone molecules, suggested by the DFT simulation results. The above conclusions are beneficial for the development of potential CO 2 capture absorbents. In addition, the industrial application feasibility of surveyed ketone absorbents is also discussed.
✓ 已验证
产品关联
DOI
高影响因子
Chem
·
2023
·
IF 23.5
Rongming Cai,Mingzi Sun,Fei Yang,Min Ju,Yanpeng Chen,M. Danny Gu,Bolong Huang,Shihe Yang
Summary By leveraging a Cu(OH)F precursor, we construct a disk-like Cu(I)/Cu(0) interface model (P-Cu x /Cu 2 OF) composed of F-stabilized Cu(I) shell and Cu(0) core by one-step pulsed potential conversion. The interfacial region is shown to facilitate ethanol formation, guaranteeing a high FE(C 2+ ) of up to 80.2%. Tuning the Cu(I)/Cu(0) ratio enhances the ethanol yield by 18.5-fold over pure P-Cu, with the corresponding partial current density (j ethanol ) reaching up to 128 mA/cm 2 . This is enabled by a 3.6-fold boost in selectivity for the ethanol product (35.4%) and an overall 7.8-fold boost in activity ( j C 2 + up to 288 mA/cm 2 ). The interactions between P-Cu and Cu 2 OF upshift the d-band center of Cu sites on the interface region, which is critical to asymmetrical C-C coupling to form OCCOH∗, concurrent with a lowered energy barrier for ethanol formation. On the other hand, the ethylene-forming symmetrical C-C coupling occurs primarily on P-Cu away from the Cu(I)/Cu(0) interface.
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2023
·
IF 12.9
Meilin Yin,LiPeng Wang,Shaokun Tang
Covalent organic frameworks (COFs) are a class of promising porous crystalline materials for both capturing and converting CO2 into high-value-added products. However, long synthesis time and the need for cocatalyst restrict its potential for CO2 conversion. Herein, bipyridine-based TAPT-BP-COF with high crystallinity as a skeleton is rapidly synthesized within only 1 h by the aid of supercritical CO2 (scCO2) activation. Then, the production of dicationic TAPT-BP2+-COF is accomplished by a quaternization reaction. The CO2 capture capacity of TAPT-BP2+-COF improved by 55.6% due to its CO2-philic groups (imine and triazine groups), polar groups (−OH), charged skeleton, and suitable pore size, thus ensuring sufficient CO2 around the catalytic active sites. Additionally, the outstanding structure-enhanced CO2 conversion performance is observed due to the presence of the synergistic effect between –OH and Br– in the TAPT-BP2+-COF skeleton. The rate-determining step of cycloaddition is significantly accelerated without any solvents and cocatalysts compared to individual TAPT-BP-COF and [OH-BP]2+[Br]2– (BP2+ moiety). Specifically, TAPT-BP2+-COF efficiently generates cyclic carbonate by heterogeneously catalyzing CO2-epoxide cycloaddition with the yield of 99.3% and has excellent stability that can be reused ten times without significant activity reduction. This work provides a novel perspective for the targeted design and rapid synthesis of charged dicationic COF-based catalysts for high efficiency and durability in CO2 capture and conversion.
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Yuqi Zhang,Di Zhang,Pengwei Lei,Ziyan Yang,Zhikun Zhang
Metal-organic frameworks (MOFs) are a promising material for CO 2 adsorption because of their great specific surface area, well-ordered porous structures ordered porous structure and various means available for functionalization. In this work, the calcium squarate (UTSA-280) was synthesized from carbide slag without pretreatment at room temperature by a rapid mechanochemical method, and then was further functionalized with tetraethylenepentamine (TEPA) to prepare CO 2 adsorbents. The effects of water content, ball milling frequency, adsorption temperature, and TEPA loading on CO 2 adsorption performance of various adsorbents were investigated. The results showed that the CO 2 adsorption of the synthesized MOFs increased firstly and then decreased with increasing water content and ball milling frequency. The synthesized MOFs with water content of 300 mmol and ball milling frequency of 15 HZ exhibited the best crystallinity. The addition of TEPA provided additional adsorption sites and led to the increase of CO 2 adsorption capacity. The UTSA-280–300-15-40TEPA demonstrated the highest CO 2 adsorption capacity (2.89 mmol/g) at 25 °C. The CO 2 adsorption kinetics analysis showed that the Avrami model fitted well with the experimental results. Furthermore, the UTSA-280–300-15-40TEPA exhibited excellent chemical stability during the adsorption–desorption cycles, with only a 14.53 % decrease in adsorption capacity after 10 cycles. This work demonstrated the possibility of preparing UTSA-280 using carbide slag for effective CO 2 adsorption.
✓ 已验证
产品关联
DOI
高影响因子
CHEMISTRY OF MATERIALS
·
2023
·
IF 8.6
Xuyang Li,Chengli Jiao,Xiaoqian Zhang,Xinxin Li,Xiangju Song,Yanyu Zhao,Heqing Jiang
Polyamide (PA) membranes show great application potential in the CO2 separation study. However, the PA membranes prepared by the traditional interfacial polymerization (IP) have a dense microstructure and a singularity of functional groups, making it difficult to exhibit both high CO2 permeance and selectivity. Herein, we report a new dual-modulation strategy by preparation method optimization and filler modification to improve the CO2 separation performance of the PA membranes. The PA membranes prepared by vapor–liquid IP have a loose microstructure, which greatly improves the gas permeance. The introduction of mono-(6-ethanediamine-6-deoxy)-beta-cyclodextrin (CD) can better loosen the PA microstructure, and the CO2-philic groups in the CD boost the CO2 selectivity by the facilitated transport effect. Ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate is further sealed into PA membranes to remedy the possible microvoids or defects and CD cavities of the membrane microstructure. The prepared membranes display excellent CO2 separation performance with CO2/H2, CO2/CH4, and CO2/N2 selectivity of 8.2, 45.5, and 116.9, as well as a CO2 permeance of about 320 GPU. The proposed strategy provides a facile and effective route to dual-modulated PA membranes for the study of CO2 separation and can be expanded to other macrocyclic molecules and ionic liquid systems.
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Quan Shi,Ming-Hui Chen,Ji Xiong,Ting Li,Ya-Qing Feng,Bao Zhang
2D metal − organic framework (MOF) nanosheets have been demonstrated to exhibit excellent properties and prospects in various aspects, especially in photocatalysis . However, the design and direct preparation of 2D MOF photocatalyst is highly desirable but still challenging. Herein, a novel 2D porphyrin-based MOF Fe-DBP(Co), which is assembled by dicarboxylic porphyrin ligands and the unprecedented undecametallic ferric-oxo clusters, is designed and developed. The unique nanosheet morphology and assembled layered structure endows the photocatalyst with higher electron-hole separation efficiency and longer photogenerated carrier lifetime compared to the analogous MOFs. Consequently, Fe-DBP(Co) exhibits strikingly excellent and stable photocatalytic performance in CO 2 cycloaddition, and the reaction rate of 103.2 mmol∙g −1 ∙h −1 is among the state-of-the-art cases for MOF-photocatalyzed CO 2 cycloaddition. The underlying mechanism investigation suggested that photogenerated electrons transferred from CoDBP ligands to the Fe clusters, and the abundant electrons and holes promoted the generation of Fe(II) and Co(III) respectively, leading to excellent catalytic performance. This work proposes a new strategy to design and develop efficient MOF photocatalysts for photocatalytic transformation of CO 2 .
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Haitao Shi,Jiajia Yang,Zia Ahmad,Haijun Zhang,Jiping Chen
Solid amine materials have emerged as a class of adsorbent with promising potential for CO 2 capture from gas mixtures, such as biogas and flue gas. In this work, we developed a novel CO 2 capture material via co-grafting of polyethyleneimine (PEI) on mesocellular silica foam (MCF), and (3-glycidyloxypropyl)triethoxysilane (GPTES) was first used as a bridging medium. In the fabrication procedure of MCF@G-35.6 %PEI, a simple impregration of PEI in MCF modified with epoxy groups was conducted. In this procedure, the co-grafting of PEI was realized in terms of a portion of PEI (21.3 wt%) was anchored on the pore surface of MCF via the epoxy/amine reaction and the rest of PEI (14.3 wt%) could be stably attached to the pore surface of MCF via its interaction with anchored PEI. After systematic evaluation, the MCF@G-35.6 %PEI exhibited a maximum CO 2 adsorption capacity of 2.78 mmol/g at 50 °C and 50 %RH and fast adsorption kinetics with equilibrium time (break through from C/C 0 = 5 % to 95 %) is 22.85 min. Meanwhile, outstanding CO 2 adsorption capabilities within a wide temperature range of 30–90 °C and a large concentration range of 5–30 % vol. CO 2 were obtained by the use of MCF@G-35.6 %PEI. More importantly, the MCF@G-35.6 %PEI also exhibited an excellent long-term stability over 50 consecutive cycles. CO 2 adsorption kinetics of the sorbent was found to follow Avrami’s fractional order model and intraparticle diffusion model. Furthermore, temperature-programmed desorption was conducted to investigate the desorption kneitics and adsorption mechanism. All these findings demonstrate the great potential of MCF@G-35.6 %PEI for carbon capture and sequestration (CCS) technology.
✓ 已验证
产品关联
DOI
高影响因子
ORGANOMETALLICS
·
2023
·
IF 2.8
Yanru Zhang,Jingjing Zhang,Ying Wang,Yang Li,Jun He,Yanyan Wang,Longbo Zhang,Zhenpeng Wang,Qingli Qian,Buxing Han
Synthesis of basic C2+ chemicals using CO2 and H2 is very promising. Herein, we present a protocol for the synthesis of different carboxylic acids by the reaction of ketones or aldehydes with CO2 and H2. The catalytic system consisted of the IrCl3 catalyst, LiI promoter, and acetic acid solvent. The yield can reach 52.9% based on the cyclohexanone substrate which can be derived from biomass. Various Cn ketones and aldehydes could be used as a substrate in the reaction, where the corresponding Cn+1 carboxylic acids were obtained. According to the mechanistic study, the reaction involved substrate conversion, reverse water–gas shift (RWGS) reaction, and carbonylation. This strategy provides an optional way of carboxylic acid production and CO2 utilization.
✓ 已验证
产品关联
DOI
高影响因子
MOLECULES
·
2023
·Vol. 28
·期 17
·6276
·
IF 4.6
Yanxi Li,Yuhua Bai,Zhuozheng Wang,Qihan Gong,Mengchen Li,Yawen Bo,Hua Xu,Guiyuan Jiang,Kebin Chi
Developing metal–organic framework (MOF) adsorbents with excellent performance and robust stability is of critical importance to reduce CO2emissions yet challenging. Herein, a robust ultra-microporous MOF, Cu(bpfb)(bdc), with mixed ligands of N, N′-(1,4-phenylene)diisonicotinamide (bpfb), and 1,4-dicarboxybenzene (bdc) was delicately constructed. Structurally, this material possesses double-interpenetrated frameworks formed by two staggered, independent frameworks, resulting in two types of narrow ultra-micropores of 3.4 × 5.0 and 4.2 × 12.8 Å2, respectively. The above structural properties make its highly selective separation at 273~298 K with a CO2capacity of 71.0~86.2 mg/g. Its adsorption heat over CO2and IAST selectivity were calculated to be 27 kJ/mol and 52.2, respectively. Remarkably, cyclic breakthrough experiments corroborate its impressive performance in CO2/N2separation in not only dry but also 75% RH humid conditions. Molecular simulation reveals that C-H···OCO2in the pores plays a pivotal role in the high selectivity of CO2adsorption. These results point out the huge potential application of this material for CO2/N2separation.Keywords:metal–organic frameworks;ultra-microporous;robust;breakthrough;CO2capture
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ChemNanoMat
·
2023
·Vol. 10
·期 3
·e202300479
·
IF 3.8
Zijian Wang,Mengdie Li,Mingjiao Xiao,Yanze Wei,Ranbo Yu,Zumin Wang
Graphical Tiny NiP nanoparticles dispersed was used as an inexpensive, stable, and active cocatalysts on ultrathin Nb 2 O 5 nanosheets to replace the noble metal Pt. Owing to the extended light harvesting, enhanced carrier separation, and improved surface reaction, the NiP/Nb 2 O 5 exhibits even higher activity and selectivity towards CO 2 photocatalytic reduction. And the roles and function mechanisms of the cocatalyst were studied. Photocatalytic CO 2 reduction holds great promise to solve energy shortage and global warming. Nb 2 O 5 has demonstrated superiority in CO 2 activation and selectivity regulation, but suffers from poor light absorption ability and fast carrier recombination. To tackle these problems, we designed and synthesized ultrathin Nb 2 O 5 nanosheets which were decorated with tiny NiP nanoparticles as cocatalyst. In this way, light absorption range broadened, carrier migration distance reduced, charge transfer resistance decreased, and surface reaction kinetics promoted. Consequently, the as-prepared NiP/Nb 2 O 5 showed notably enhanced activity (148.7 μmol ⋅ g −1 ) and selectivity (82.1 %) towards CO, as well as remarkable stability. This work paves the way for cheap and earth abundant alternatives as cocatalysts and deepens the understanding of their functions in CO 2 photoreduction.
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）