ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 20
·2213999
·
IF 19
Yizhong Zhang,Liuchang Wang,Ruichi Zhang,Chao He,Lixia Jia,Xunliang Wang,Xuemin Feng,Tianxiang Jiang,Baolong Xie,Xiaolei Ma,Junrui Cao,Yuhui Ma,Xin Tan,Tao Yu
Because of spontaneous agglomeration effect and undesirable electronic state of Zr sites on the surface, zirconium (hydro)oxides generally exhibit suboptimal defluoridation capacity. Herein, a template confinement-ligand anchoring strategy is developed by utilizing confined growth of zirconium hydroxide (ZH) inside chitosan hydrogel beads (CHB) and subsequent anchoring of fumaric acid (fm) on its surface Zr sites in a monodentate mononuclear coordination mode. This technique leads to uniform dispersion of ultrafine fmZH (≈3.4 nm) and tunable electron density at the Zr sites. Due to the electron-withdrawing ability of fm, electron-delocalized Zr sites increase the orbital energy level matching and vacate Zr 4d orbitals to promote hybridization with the F 2p orbitals. Ultimately, robust Zr F bond can be formed as a result of reduced the adsorption energy toward fluoride ions. The defluoridation capacity shows positive linear relationship with the electron extraction ability of ligands. The saturation adsorption capacity and dynamic treatment capacity of CHB@fmZH are 10.8 and 45.9 times higher than that of CHB@ZH, respectively, owing to high electron extraction (0.098 e − ) of fm. This study offers a novel insight into the design and synthesis of high-efficiency metal oxide adsorbents by steering its surface metal sites’ electronic state through ligand effect.
研究领域:
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2018
·
IF 4.484
Tengfei Long,Hongmei He,Jizhou Li,Mengke Yuan,Jianjia Wei,Zhongde Liu
Inspired by the knowledge that the chiroptical activity of Cu and Ag nanoclusters (NCs) is generally about several-fold larger than that of the corresponding Au NCs but poor stability and that alloy metal particles often demonstrate unique stability, in this contribution the synthesis of the chiral Au–Cu alloy NCs was attempted via reduction of varying mole fractions of metal precursors by sodium borohydride in the presence of d-/l-penicillamine (d-/l-Pen), to gain insights into the alloying effect on the chiroptical activity. As a result, the g factors of ∼0.57 × 10–3, obviously larger than that of the pure Au NCs, are found for the bimetallic Au–Cu NCs, suggesting that the incorporation of Cu heteroatoms plays a dramatic role for the creation of the strong optically active metal nanostructures. More importantly, compared with those of monometallic Cu counterparts, the optical active stability of bimetallic Au–Cu NCs is obviously improved because of the alloy formation. The location of the copper dopant, observed from the transmission electron microscopy results and deduced by the X-ray photoelectron spectroscopy measurements, can be speculated to be incorporated in both the “core” region and the “staple” region. Additionally, it was found that the different thiolated chiral molecule ligands exert influence on the chiroptical behavior of the Au–Cu NCs. Thus, the alloy formation strategy could produce novel nanostructures with the characteristic of large and stable chiroptical activity.
研究领域:
纳米材料科学
·
物理化学
·
材料化学
✓ 已验证
DOI
高影响因子
CRYSTENGCOMM
·
2023
·Vol. 25
·期 25
·3655-3661
·
IF 3.1
Ningkang Qian,Degong Ding,Liang Ji,Junjie Li,Hui Zhang,Deren Yang
Lattice engineering is a powerful strategy not only to optimize electrocatalytic performances, but also to deepen the understanding of electrocatalytic mechanisms. Lattice engineering can be effectively achieved in core–shell nanocrystals owing to the lattice mismatch of heterostructures. Herein, we constructed three kinds of icosahedra consisting of Au73Pd27@Pt, Au66Pd34@Pt and Pd@Pt core–(interlayer)–shell by a seed-mediated method. The introduction of an ultrathin Pd interlayer in the Au66Pd34@Pt icosahedra enables us to separately identify the strain effect and ligand effect. The specific activities towards the EOR of these icosahedra are in the sequence Au73Pd27@Pt > Au66Pd34@Pt > Pd@Pt, indicating that both the ligand effect and strain effect caused by Au can enhance the activity of Pt towards the EOR. The in situ FTIR studies confirm that the EOR processes on these icosahedra are all dominated by the C2 pathway, and hence we ascribe the enhancements of EOR activities to the faster kinetics of the C2 pathway by producing acetate or acetaldehyde.
研究领域:
材料科学
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电催化
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纳米技术
✓ 已验证
产品关联
DOI
高影响因子
Nano Research
·
2021
·Vol. 15
·期 2
·1472-1478
·
IF 8.897
Feng Han,Xiong Xiaohong,Gong Lele,Zhang Huiping,Xu Ying,Feng Xuefeng,Luo Feng
The reticular chemistry strategy presents a powerful molecule-design tool to tailor the physical and chemical properties of metal-organic framework (MOF). In this work, we for the first time investigated the effect of organic ligands on the radionuclide sequestration (TcO 4 − ) of thorium-organic framework. Through a coordination modulation technique, two novel isoreticular thorium-organic frameworks, namely Th-MOF-67 and Th-MOF-68, were obtained. Relative to the antetype MOF of Th-MOF-66 that shows extremely low uptake of ReO 4 − (a chemical surrogate of radioactive TcO 4 − ), the isoreticular MOFs of Th-MOF-67 and Th-MOF-68 enable ultrahigh uptake of ReO 4 − , giving an impressively 36.8-fold or 56-fold enhancement, respectively. The adsorption capacity of Th-MOF-68 is as high as 560 mg/g, exceeding most reported adsorbents for such use. The mechanism for such exceptional outstanding performance, as unveiled by both the single crystal X-ray diffraction and theoretical calculation, is due to coordination interaction for Th-MOF-67, when a tetrazolate ligand was used, or a combined effect from both coordination interaction and anion-exchange for Th-MOF-68, if using a triazolate ligand.
研究领域:
材料科学
·
环境科学
✓ 已验证
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2018
·
IF 4.521
Likai Wang,Jin Peng,Zhenghua Tang,Xiongwu Kang,Mingli Fu,Shaowei Chen
Structurally similar molecule-like Au 11 (PPh 3 ) 7 Cl 3 and [Au 11 (PPh 3 ) 8 Cl 2 ]Cl nanoclusters have been successfully synthesized and employed as catalysts for selective oxidation of styrene. The two clusters exhibited similar but slightly different well-defined optical absorbance, and the subtle structural difference is also reflected in proton nuclear magnetic resonance ( 1 H NMR) studies. In electrochemical measurements, Au 11 (PPh 3 ) 7 Cl 3 and [Au 11 (PPh 3 ) 8 Cl 2 ]Cl show a large electrochemical band gap of 2.15 eV and 2.09 eV, respectively. Styrene oxidation has been employed as a model reaction to investigate the impacts of the ligand shell composition on the catalytic activity and selectivity of the two clusters. Interestingly, the main product is benzaldehyde when oxygen is employed as oxidant, and the catalytic activity of Au 11 (PPh 3 ) 7 Cl 3 is higher than that of [Au 11 (PPh 3 ) 8 Cl 2 ]Cl. Under the same conditions, the two Au 11 clusters exhibit much higher catalytic activity than larger clusters (Au 25 , Au 38 and Au 144 ) capped with phenylethiolates, as a manifestation of both size influence and surface ligand impacts. In addition, the oxidation efficiency of styrene exhibit a sharp increase when tert-butyl hydroperoxide is utilized as the oxidant, where the catalytic activities of Au 11 (PPh 3 ) 7 Cl 3 and [Au 11 (PPh 3 ) 8 Cl 2 ]Cl are comparable with styrene epoxide being the major product. Finally, the twin clusters are either reduced or oxidized to probe the charge effects upon the catalytic reaction, and it was found that the conversion of styrene went up with the charge state from reduced to oxidized for both clusters.
研究领域:
化学
·
催化科学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INORGANIC CHEMISTRY
·
2025
·
IF 4.7
Jianye Wang,Zengxuan Chen,Xiaojing Lin,Zhaojie Wang,Xiaodong Chen,Xingheng Zhang,Jiao Li,Jinpeng Liu,Siyuan Liu,Shuxian Wei,Daofeng Sun,Xiaoqing Lu
Mismatched electron and proton transport rates impede the manifestation of effective performance of the electrocatalytic oxygen evolution reaction (OER), thereby limiting its industrial applications. Inspired by the natural protein cluster in PS-II, different organic–inorganic hybrid electrocatalysts were synthesized via a hydrothermal method. p-Toluidine (PT), benzoic acid (BA), and p-aminobenzoic acid (PABA) were successfully intercalated into NiFe-LDH. Compared to the organic molecules containing a single functional group, the coexistence of carboxyl and amino groups served as the electron acceptor and donor, respectively, thereby optimizing the electronic structure and suppressing metal dissolution. The overpotential of the PABA-modified catalyst (NiFe-LDH-PABA) was significantly reduced to 225 mV at 10 mA cm–2, and the Tafel slope was only 38.7 mV dec–1. At a high current density of 500 mA cm–2, the NiFe-LDH-PABA catalyst can work stably in a 1 M KOH solution at 25 °C over 550 h with 96% retention of its initial activity. Density functional theory (DFT) calculations further confirmed that the work offers significant insight into the modulation by organic molecular structure and provides a new paradigm for creating organic–inorganic hybrid OER catalysts.
研究领域:
电催化
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材料科学
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理论计算
✓ 已验证
DOI
PubMed
高影响因子
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
·
2024
·Vol. 121
·期 17
·e2318853121
·
IF 9.4
Junliang Chen,Fangzhou Zhang,Min Kuang,Li Wang,Huaping Wang,Wei Li,Jianping Yang
Recently, there has been a notable surge in interest regarding reclaiming valuable chemicals from waste plastics. However, the energy-intensive conventional thermal catalysis does not align with the concept of sustainable development. Herein, we report a sustainable electrocatalytic approach allowing the selective synthesis of glycolic acid (GA) from waste polyethylene terephthalate (PET) over a Pd67Ag33 alloy catalyst under ambient conditions. Notably, Pd67Ag33 delivers a high mass activity of 9.7 A mgPd−1 for ethylene glycol oxidation reaction (EGOR) and GA Faradaic efficiency of 92.7 %, representing the most active catalyst for selective GA synthesis. In situ experiments and computational simulations uncover that ligand effect induced by Ag incorporation enhances the GA selectivity by facilitating carbonyl intermediates desorption, while the lattice mismatch-triggered tensile strain optimizes the adsorption of *OH species to boost reaction kinetics. This work unveils the synergistic of strain and ligand effect in alloy catalyst and provides guidance for the design of future catalysts for PET upcycling. We further investigate the versatility of Pd67Ag33 catalyst on CO2 reduction reaction (CO2RR) and assemble EGOR//CO2RR integrated electrolyzer, presenting a pioneering demonstration for reforming waste carbon resource (i.e., PET and CO2) into high-value chemicals.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MATERIALS SCIENCE
·
2022
·Vol. 57
·期 14
·7276-7289
·
IF 4.682
Wang Yonghan,Hu Feng,Chen Ying,Wang Hui,Fetohi Amani E.,Hao Yanan,Li Linlin,El-Khatib K. M.,Peng Shengjie
Electrocatalytic conversion from carbon dioxide with main products of carbon monoxide and hydrogen provides an economic and sustainable pathway to produce syngas, while the involved electrocatalysts with high activity and stability as well as highly tunability for CO/H 2 ratio are still rare. Here, we report a facile method to prepare palladium (Pd) nanoparticle ensembles with unique three-dimentional (3D) architecture and porosity as well as plenty of grain boundaries, which are electrocatalytically active for electrochemical carbon dioxide reduction (eCO 2 RR) to syngas. At the potential of − 0.8 V (versus reversible hydrogen electrode), the CO selectivity of such Pd nanoparticle ensembles is up to ca. 90% and the CO/H 2 ratio can be adjusted from one to six by varying the applied potentials. The syngas production on Pd nanoparticle ensembles can be further regulated by changing the reaction temperature and modified ligands. This method for fabricating Pd nanoparticle ensembles with rational tenability paves the way for the fundamental research and commercial deployment of eCO 2 RR and syngas production. Graphical abstract Pd nanoparticle ensembles with grain boundaries and high porosity were developed for tunable CO 2 conversion to syngas under ligand exchange and temperature control.
研究领域:
材料科学
·
电化学
·
能源转换
✓ 已验证
DOI
高影响因子
Coatings
·
2024
·Vol. 14
·期 4
·439
·
IF 2.9
Xi Quan,Pengzhao Lv,Linlin Yin,Wei Zuo,Yu Tian,Jun Zhang
This study presents a detailed investigation into the use of β-cyclodextrin (β-CD) encapsulated iron oxide nanoparticle (β-CD@Fe3O4) composites, modified with different ligands, to activate peroxymonosulfate (PMS) for the degradation of pharmaceutical contaminants, namely, diclofenac, carbamazepine, and erythromycin. The focus is on understanding the ligand effect, particularly using citric acid (CIT), polyethyleneimine (PEI), and cetyl trimethyl ammonium bromide (CTAB), on the degradation performance of these composites. Employing density functional theory (DFT) calculations, this work examines the electronic structure and charge distributions of β-CD@Fe3O4composites, providing insights into their interaction with various pollutants. The study reveals that the β-CD@PEI@Fe3O4composite demonstrates superior degradation efficiency due to optimal electrostatic interactions, regardless of the pollutant’s hydrophobicity. On the other hand, β-CD@CIT@Fe3O4shows moderate efficiency, and β-CD@CTAB@Fe3O4exhibits selective efficiency, particularly for hydrophobic compounds. These findings underscore the significant role of surface chemistry in modulating the activation of PMS and the degradation of contaminants, opening avenues for designing tailored β-CD composites for environmental remediation.
研究领域:
环境科学
·
材料科学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Lizhang Chen,Xuan Wang,Tingyu Lu,Huan Pang,Songtao Zhang,Lin Xu,Gaixiu Yang,Qixing Zhou,Yawen Tang
As one of the most competitive alternatives to precious Pt-based electrocatalysts towards the oxygen reduction reaction (ORR), Fe-N-C single atom catalysts (SACs) are still eagerly anticipated to undergo further performance enhancement to advance their practical applications in diverse renewable energy systems. The regulation of energy level of Fe site through the manipulation of d-orbital splitting manner provides a novel route to improve the intrinsic activity, yet still in its infancy. We herein present a Fe d-orbital splitting modulation strategy via crafting atomically dispersed Fe-N 5 moieties with axial N ligand anchored on “lotus root”-like N-doped multichannel carbon nanofibers (abbreviated as FeN 5 @NMCNFs hereafter). Symmetrical experimental and theoretical findings reveal that near-range coordinated effect of axial N ligand results in the deformation of local symmetry, deep valence band spin-polarization of d orbitals and downshifted d-band center of Fe center site, endowing the optimized adsorption energetics of ORR intermediates and reduced reaction energy barrier. Accordingly, the as-developed FeN 5 @NMCNFs deliver Pt-competitive ORR activity and extraordinary long-term durability in KOH electrolyte with a halfwave potential of 0.87 V, exceeding a majority of recently reported non-precious SACs. Furthermore, when incorporated into liquid and flexible all-solid-state Zn air batteries (ZABs), the FeN 5 @NMCNFs||RuO 2 -assembled ZABs demonstrate superior electrochemical performance to the state-of-the-art Pt/C||RuO 2 counterpart. This work offers a new perspective for the performance optimization of SACs via the manipulation of the local coordination manner and the precise spin-polarization regulation strategy.
研究领域:
材料科学
·
电催化
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2017
·
IF 4.233
Qing Qing Xia,Lian Ying Zhang,Zhi Liang Zhao,Chang Ming Li
Uniform Pt 1 Ru 0.5 Sn 0.5 ternary alloy nanoparticles are in situ deposited on reduced graphene oxide (Pt 1 Ru 0.5 Sn 0.5 -RGO) through its functional groups and defects as nucleation sites to greatly electrocatalyze ethanol oxidation reaction for much higher mass current densities, larger apparent specific current densities and better stability than commercial Pt-C catalyst (Pt-C(commer)). Mechanistic studies indicate that the excellent electrocatalytic activity and anti-poisoning are resulted from a strong ligand effect of the ternary alloy components, in which the charge transfer is boosted while decreasing the density of states close to the Fermi level of Pt to reduce bond energy between Pt and CO-like adsorbates for greatly improved anti-poisoning ability. This work holds a great promise to fabricate a high performance anode catalyst with a low Pt loading for direct ethanol fuel cells.
研究领域:
材料科学
·
电化学
·
能源科学
✓ 已验证
DOI
高影响因子
ACS Nano
·
2024
·
IF 15.8
Shuai Zhang,Leilei Yin,Qian Liu,Guangtong Hai,Yaping Du
The ligand effect in alloy catalysts is one of the decisive parameters of the catalytic performance. However, the strong interrelation between the ligand effect and the geometric effect of the active atom and its neighbors as well as the systematic alteration of the microenvironment of the active site makes the active mechanism unclear. Herein, Pt3Tm, Pt3Yb, and Pt3Lu with a cubic crystal system (Pm-3m) were selected. With the difference of Pt−Pt interatomic distance within 0.02 Å, we minimize the geometric effect to realize the disentanglement of the system. Through precise characterization, due to the low electronegativity of Ln (Ln = Tm, Yb, and Lu) and the ligand effect in the alloy, the electronic structure of Pt is continuously optimized, which improves the electrochemical methanol oxidation reaction (MOR) performance. The Ln electronegativity has a linear relationship with the MOR performance, and Pt3Yb/C achieves a high mass activity of up to 11.61 A mgPt−1, which is the highest value reported so far in Pt-based electrocatalysts. The results obtained in this study provide fundamental insights into the mechanism of ligand effects on the enhancement of electrochemical activity in rare-earth nanoalloys.
研究领域:
材料科学
·
催化
·
电化学
·
纳米技术
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）