FUEL
·
2025
·
IF 7.5
Wensheng Wei,Yuxin Wang,Guangwen Xu,Jinggang Zhao,Lei Shi
A series of novel imidazolium-based cationic metal complexes ([EIMBr-COO] n M, n = 1, 2, 3, 4 and M = Mg 2+ , Al 3+ , Ca 2+ , Ti 4+ , V 2+ , Cr 3+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zr 4+ , Ag 1+ , Sb 3+ , Pb 2+ , La 3+ and Ce 3+ ) were successfully constructed through coordination-driven self-assembly by an efficient one-step grinding strategy. This self-assembly process occurs when hydroxyl oxygen atoms from [ECOOHIM]Br ligand donate electron pairs to empty orbitals in the metal ions, resulting in the formation of stable complexes. Notably, the prepared [EIMBr-COO] 2 Zn catalyst displayed excellent catalytic activity in the cycloaddition reaction of propylene oxide (PO) and CO 2 , and the propylene carbonate (PC) yield reached 83.55% with a TOF of 1461 h −1 within only 10 min. The synergistic effects of Zn 2+ centers (Lewis acid), imidazolinium groups (Lewis base) and Br - ions (nucleophilic site) in [EIMBr-COO] 2 Zn contributed the excellent catalytic performance. Meanwhile, the formation of a chemical bond (Zn-O) through the coordination-driven self-assembly strategy guarantees its stability. Moreover, a rational dual-activation mechanism of Lewis acid and Br - centers was proposed based on density functional theory calculations (DFT) to explain the acceleration mechanism of the rate-determining step. Besides, [EIMBr-COO] 2 Zn showed a wide range of catalytic universality in cycloaddition reactions and satisfactory stability. Therefore, this study is expected to present theoretical and practical support for the design and synthesis methodology of multifunction catalysts for CO 2 cycloaddition.
研究领域:
化学
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2024
·
IF 4.3
Mengyuan Jin,Xiang Han,Aitong Yang,Ting Chou,Tingting Chen,Yecan Pi,Shun Wang,Yun Yang,Juan Wang,Huile Jin
Interfacial engineering is considered an effective strategy to improve the electrochemical water-splitting activity of catalysts by modulating the local electronic structure to expose more active sites. Therefore, we report a platinum–cobaltic oxide nanosheets (Pt/Co3O4 NSs) with plentiful grain boundary as the efficient bifunctional electrocatalyst for water splitting. The Pt/Co3O4 NSs exhibit a low overpotential of 55 and 201 mV at a current density of 10 mA cm–2 for the hydrogen evolution reaction and oxygen evolution reaction in 1.0 M potassium hydroxide, respectively. A negligible degradation of 1.52 V at a current density of 10 mA cm–2 after continuous operation for 100 h, demonstrates the long-term stability of the catalyst. Furthermore, the overall water-splitting performance of the Pt/Co3O4 NSs surpasses that of the commercial Pt/C||RuO2. The density functional theory calculation results explain that the improvement of catalyst activity is attributed to the moderate adsorption/desorption energy of *H and the low reaction energy barrier of the rate-determining step. This work presents a novel vision to design bifunctional catalysts for the storage and conversion of hydrogen energy.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Guokai Cui,Shuzhen Lyu,Fengtao Zhang,Huiyong Wang,Zhiyong Li,Yanan Li,Jianji Wang
In this contribution, a series of ionic liquids (ILs) with tri-n-butylethyl-phosphonium cation ([P4442]) and functional anions are designed and prepared, including pyridinolate anion ([PyO]), pyridinecarboxylate anion ([PyCOO]), and pyridinesulfonate anion ([PySO3]). Each anion contains both N site and O site, which can react with SO2. It could be found that up to 4.71 mol SO2 mol–1 IL absorption capacity could be received by [P4442][PyO] at 20 °C and 1 bar. Compared to ILs with phenolate anion ([PhO]), benzoate anion ([PhCOO]), and benzenesulfonate anion ([PhSO3]), the pyridine-based counterparts in this work were found to significantly enhance SO2 capture capacity, especially for anions with high basicity. It was demonstrated from the combination of FT-IR and NMR spectroscopic investigations and DFT calculations that the simultaneous cooperative interaction of N···SO2 and O···SO2 between functional anion [PyO] and SO2 was the main reason for high absorption capacity of low-concentration SO2 by [P4442][PyO].
研究领域:
化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Abdul Qayum,Xiang Peng,Jianfa Yuan,Yuanduo Qu,Jianhong Zhou,Zanling Huang,Hong Xia,Zhi Liu,Daniel Qi Tan,Paul K. Chu,Fushen Lu,Liangsheng Hu
Ni-/Fe-based materials are promising electrocatalysts for the oxygen evolution reaction (OER) but usually are not suitable for the hydrogen evolution reaction (HER). Herein, a durable and bifunctional catalyst consisting of Ni-FeOx and FeNi3 is prepared on nickel foam (Ni-FeOx/FeNi3/NF) by in situ solution combustion and subsequent calcination to accomplish efficient alkaline water splitting. Density functional theory (DFT) calculation shows that the high HER activity is attributed to the strong electronic coupling effects between FeOx and FeNi3 in the Janus nanoparticles by modulating ΔGH* and electronic states. Consequently, small overpotentials (η) of 71 and 272 mV in HER and 269 and 405 mV in OER yield current densities (j) of 50 and 1000 mA cm–2, respectively. The catalyst shows outstanding stability for 280 and 200 h in HER and OER at a j of ∼50 mA cm–2. Also, the robustness and mechanical stability of the electrode at an elevated j of ∼500 mA cm–2 are excellent. Moreover, Ni-FeOx/FeNi3/NF shows excellent water splitting activities as a bifunctional catalyst as exemplified by j of 50 and 500 mA cm–2 at cell voltages of 1.58 and 1.80 V, respectively. The Ni-FeOx/FeNi3/NF structure synthesized by the novel, simple, and scalable strategy has large potential in commercial water electrolysis, and the in situ combustion method holds great promise in the fabrication of thin-film electrodes for different applications.
研究领域:
材料科学
·
电化学
·
理论计算
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Applied Nano Materials
·
2023
·
IF 5.9
Yaohui Gao,Wenjun He,Da Cao,Fangqing Wang,Ying Li,Qiuyan Hao,Caichi Liu,Hui Liu
Designing effective and low-cost bifunctional electrocatalysts for the alkaline hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is essential to achieve green development of the hydrogen economy. Herein, we have developed Mo-doped Ni3S2 nanosheet array catalysts with excellent electrochemical properties. Only 85 mV (HER) and 230 mV (OER) overpotentials are required under alkaline conditions at 10 mA cm–2 and remain undegraded for 100 h. In addition, it only required 1.52 V at 10 mA cm–2 in an alkaline electrolyzer, and it remained unchanged for more than 100 h in stability tests, outperforming most reported electrocatalysts. Experiments and density functional theory (DFT) calculations confirmed that the doping of Mo could expose more active sites of Ni3S2 and optimize the adsorption free energy of the intermediate, which in turn improves its intrinsic activity. This work reveals the key role of Mo in Ni3S2 electrocatalytic performance enhancement at the atomic scale.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
Surfaces and Interfaces
·
2023
·
IF 6.2
Lei Zhou,Xiangyu Xi,Haidong Li,Han Song,Qiong Mei,Yuankun Yang,Shu Chen,Qunwei Dai,Faqin Dong
Vanadium contamination has gained increasing attention around the world and it is urgent to develop feasible approach to tackle this growing pollution (e.g., vanadate). Herein, density functional theory (DFT) calculations combined with batch experiments were used to systematically evaluate the capacity of Mg(OH) 2 to adsorb vanadate , by investigating the impacts of different exposed facet and surface OH defect on the structure configurations, adsorption energy and the efficiency of vanadate adsorption. DFT calculations suggested that although the capacity of vanadate adsorption on the facets of Mg(OH) 2 would be obviously influenced by the formation of various coordination complex (e.g., monodentate, bidentate and tridentate) on each facet, the capacity for these facets of Mg(OH) 2 towards vanadate adsorption followed the order: (100) > (001). Moreover, such a vanadate adsorption was further enhanced by the presence of surface OH defect, owing to altered densities of states (DOS) of the adsorption site. Batch experiments verified the defect-rich Mg(OH) 2 was favorable to adsorb vanadate, and both (001) and (100) facet play the great roles. This molecular-level understanding of the facet-dependent and defect-enhanced adsorption behavior of Mg(OH) 2 toward vanadate provides a useful insight into designing and applying effective adsorbents for the removal of heavy metal oxyanions.
研究领域:
环境科学
·
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Shandi Zhong,Cai Xu,Quanfu Long,Hang Zhou,Jianhai Yang,Jia Guo,Xiaozhong Wang,Liyan Dai
Using O 2 as an oxidant, developing a non-noble metal catalyst for the selective catalytic C–H bond oxidation of p-chlorotoluene is desirable and challenging. In this work, a series of Co, Cr co-doped OMS-2 (Octahedral Molecular Sieve-2) catalysts were prepared by a conventional refluxing method. It was found that the incorporation of Co and Cr improved the catalytic activity for the selective oxidation of p-chlorotoluene to p-chlorobenzaldehyde. Among these catalysts, CoCr/OMS-2 (Co: Cr = 1: 1, mass ratio), the best catalyst, shows that the conversion and the selectivity of p-chlorobenzaldehyde is 94.8 % and 94.3 %, respectively. The enhanced catalytic activity was due to the larger specific surface area and even dispersion of active components. The characterization results also disclosed that the co-doping of Co and Cr increased the oxygen vacancy and enhanced the ability to activate the surface lattice oxygen. Additionally, density functional theory calculations demonstrated that co-doping of Co and Cr promoted the adsorption of p-chlorotoluene and O 2 , and decreased the energy barrier of rate-determining step (the conversion of p-chlorobenzyl alcohol to p-chlorobenzaldehyde). Besides, when H 2 O was added to the reaction system as the second solvent, the activation and dissociation of O 2 , and the formation of p-chlorobenzaldehyde were facilitated, in agreement with the experimental results. This work demonstrated the promotional effect of Co, Cr co-doped into OMS-2 catalyst and the role of H 2 O for the selective oxidation of p-chlorotoluene.
研究领域:
催化化学
·
材料科学
·
环境化学
✓ 已验证
产品关联
DOI
高影响因子
Advanced Science
·
2020
·Vol. 7
·期 5
·1902830
·
IF 15.84
Ruchun Li,Bihua Hu,Tongwen Yu,Haixin Chen,Yi Wang,Shuqin Song
Rational design of unique pre-catalysts for highly active catalysts toward catalyzing the oxygen evolution reaction (OER) is a great challenge. Herein, a Co-derived pre-catalyst that allows gradual exposure of CoOOH that acts as the active center for OER catalysis is obtained by both phosphate ion surface functionalization and Mo inner doping. The obtained catalyst reveals an excellent OER activity with a low overpotential of 265 mV at a current density of 10 mA cm −2 and good durability in alkaline electrolyte, which is comparable to the majority of Co-based OER catalysts. Specifically, the surface functionalization produces lots of Co-PO 4 species with oxygen vacancies which can trigger the surface self-reconstruction of pre-catalyst for a favorable OER reaction. Density functional theory calculations reveal that the Mo doping optimizes adsorption-free energy of *OOH formation and thus accelerates intrinsic electrocatalytic activity. Expanding on these explorations, a series of transition metal oxide pre-catalysts are obtained using this general design strategy. The work offers a fundamental understanding toward the correlation among surface-structure-activity for the pre-catalyst design.
研究领域:
材料科学
·
电催化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CATALYSIS TODAY
·
2022
·
IF 6.562
Gongguo Zhang,Yingying Wang,Yanyun Ma,Yiqun Zheng,Haifeng Zhang,Mingyu Tang,Yunqian Dai
We report the fabrication of PdSm bimetallic nanocrystals with controlled shapes and explore their applications as the electrocatalysts for electroxidation of ethanol (EOR) in alkaline medium. The success of current synthesis relies on the co-reduction of Pd(acac) 2 and Sm(acac) 3 in the presence of N-oleyl-1,3-propanediamine (OPDA) and Mo(CO) 6 at an elevated temperature. For the first time, ultrathin nanostructures composed of Pd-rare earth metal bimetals could be prepared in high purity, in the form of ultrathin porous nanosheets and concave tetrahedra, together with the size/edge length limited to sub-3 nm size range. When serving as electrocatalysts for EOR, the carbon-supported PdSm nanocrystals exhibited in seven-fold increase in mass activity as compared to that of Pt/C, as well as improved reaction kinetics and long-term durability. DFT calculations verify that the PdSm NCs/C catalyst modulate the reaction pathway of ethanol oxidation with lower energy barriers as compared with Pd catalyst, accounting for the improved catalytic performance. The present study provides a feasible strategy to create rare earth metal-doped bimetallic nanocrystals with controlled morphology for rational design over fuel cell catalysts and could be extended to other noble metals or alloys.
研究领域:
材料科学
·
电化学
·
催化科学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2019
·
IF 4.084
Yating Xie,Ligang Chen,Qiu Jin,Jimmy Yun,Xin Liang
Co–Mo–S based catalysts have promising applications in both hydrogen evolution reaction (HER) and hydrodesulfurization (HDS). Herein, MoS 2 –Co 3 S 4 hollow polyhedrons have been successfully synthesized by the vulcanization of Mo doped ZIF-67. MoS 2 –Co 3 S 4 hollow polyhedrons show the superior HER and HDS catalytic activities to pure MoS 2 , Co 3 S 4 and MoS 2 –Co 3 S 4 nanoparticles prepared by the traditional coprecipitation methods, owing to the both morphology effect and synergistic effect between Co 3 S 4 and MoS 2 . DFT calculation studied the activation energies needed by MoS 2 and Co–Mo–S for HER and HDS, respectively. The required activation energies for C–S bond fracture and H 2 generation on Co–Mo–S structure are both obviously lower than that of MoS 2 structure. Our work reported a new method to synthesize Co–Mo–S catalysts with large surface area and numerous active sites, and further experimentally and theoretically proved Co–Mo–S structure had better catalytic activities for both HER and HDS.
研究领域:
材料科学
·
催化化学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2023
·
IF 22.1
Yayun Pu,Yufei Liu,Xiaosheng Tang,Qiang Huang,Limin Huang
Realizing bifunctional catalysts for the HER and OER in a unified environment bears the promising goal of reducing the cost and complexity of electrolyzer devices. Dual atoms configuration intrinsically active to hydrogen/oxygen evolution is a feasible way to achieve that target. In this work, Co, Ir active species were selected to be inserted into the interlayer space of layered V 2 O 5 , forming a two-dimensional confined structure that significantly improves the atomic efficiency. During the electrochemical water splitting in alkaline medium, the V-O framework that encapsulated the active species in layered V 2 O 5 was collapsed and disrupted due to its acidic nature. The HER/OER active Co, Ir were readily released and exposed to the reactant. In situ structure evolution was monitored and elaborately analyzed by operando Raman, TEM and XPS characterizations. Further, DFT calculation disclosed that the Co atom was covalently stabilized by the nearest oxygen that leads to electron-depleted Co. The stabilization of Ir was achieved by forming both a covalent bond with oxygen and a metallic bond with sublayer V. This, however, resulted in a changed electron distribution in Ir, leading to better binding with oxygenate intermediates and improved OER activity. As for the alkaline HER, the potential determining step (PDS) of IrCo@V 2 O 5 is predominately determined as the OH desorption, regardless of the H evolution pathway of Volmer-Tafel or Volmer-Heyrovsky. The bifunctional IrCo@V 2 O 5 acted like a “Trojan Horse” and achieved an ultrahigh mass activity of 848 A g -1 Co,Ir for the OER and 461 A g -1 Co,Ir for the HER. This work provides new insight into creating highly effective electrocatalysts via the in situ releasing methodology.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Yasen Dai,Xiaolei Song,Zerou Wang,Shuhang Ren,Yucui Hou,Weize Wu
Hydrogen sulfide (H 2 S) is a highly toxic and corrosive pollutant threatening human health and the environment. Ionic liquids (ILs) are widely used for H 2 S capture, but existing research focuses on conventional or alkaline functional ILs with low capacity or high energy consumption. This work synthesizes a novel oxidative functional IL, tetraethylammonium metavanadate ([N 2222 ][VO 3 ]), for dilute H 2 S absorption. With [Bmim][BF 4 ] as solvent, the mixture absorbs 1.13 mol H 2 S/mol IL at 50 °C and 0.005 MPa partial pressure. The IL mixture converts H 2 S to sulfur and water in situ and regenerates completely with oxygen at 80 °C for five cycles without capacity loss. Characterization and DFT calculations confirm vanadium’s key role in oxidative absorption, changing from V 5+ to V 3+ . The mechanism is verified at the molecular level. The mild regeneration temperature and sulfur recovery offer a scalable solution for low-energy desulfurization processes.
研究领域:
环境科学
·
化学工程
·
材料科学
·
物理化学
✓ 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）