JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
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IF 9.4
Junhua Kuang,Shuaishuai Zhang,Jia Yu,Yuting Zhang,Chun-Kuo Peng,Chen Zou,Jiaran Li,Li Peng,Lu Lin,Yan-Gu Lin,Pengbo Lyu,Shuliang Yang,Jian-Feng Li
Iron, one of the most abundant elements on earth and an essential element for living organisms, plays a crucial role in our daily metabolism. In the field of catalysis, the development of high-performance catalysts based on less toxic iron element is also of significant importance for green chemistry and a sustainable future. To construct Fe-based heterogeneous catalysts with excellent hydrogenation performance, precise modulation of the atomic coordination structure is a key strategy for enhancing catalytic activity. In this study, we present an in-situ coating method for applying a zeolitic imidazolate framework (ZIF) onto the surface of fungal hyphae. The asymmetric coordination structure of Fe 1 -N 3 P 1 was precisely tailored by utilizing the phosphorus source from the fungus and the nitrogen source in the ZIFs. Detailed characterizations and density functional theory calculations revealed that the incorporation of ZIFs not only increased the specific surface area of catalysts, but also facilitated the dispersion of Fe 2 P nanoparticles into the Fe 1 -N 3 P 1 center, making the lowest reaction energy barrier and resulting in the best performance for nitrobenzene hydrogenation when compared to the Fe 2 P nanoparticles and clusters. This research introduces a novel design concept for constructing asymmetric monoatomic configuration based on the inherent characteristics of natural microorganisms and the exogenous porous coordination polymers.
研究领域:
催化化学
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材料科学
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环境科学
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产品关联
DOI
PubMed
高影响因子
ACS ES&T Engineering
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2024
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IF 7.4
Lan-Ying Liu,Min-Hua Cui,Shi-Ming Niu,Xue-Dong Zhang,Xin-Hui Li,Wo-Long Wang,He Liu,Guo-Shuai Liu,Ai-Jie Wang
In this study, we synthesized a phosphorus-coordinated Pd@MXene catalyst to address the drawbacks associated with high noble metal usage, susceptibility to poisoning, and stability issues in the electrocatalytic hydrodehalogenation (EHDC) of recalcitrant halogenated pollutants. The phosphorus-coordinated Pd@MXene exhibited an EHDC performance comparable to that of the benchmark electrode (Pd@MX/CC) when tested on the model pollutant diclofenac (DCF). Notably, the phosphorus-coordinated Pd electrode demonstrated an 80% reduction in Pd usage and a 3.9-fold increase in Pd utilization efficiency. This improved performance was consistent across a wide range of pH values (pH 3, 7, and 11) and was sustained over 10 reaction cycles for the removal of DCF. Furthermore, the enhanced catalytic activity of the phosphorus-coordinated Pd electrode was achieved in the EHDC of various halogenated compounds. Importantly, the electrode exhibited a favorable tolerance to inorganic ions during the EHDC process. Density functional theory (DFT) calculations provided insights into the electronic configuration regulation of phosphorus-coordinated Pd@MXene, optimizing binding energies for H* and dechlorinated intermediates. The reported promotion effect of halogenated pollutants degradation by the phosphorus-coordination approach offers new insights into efficient EHDC systems toward water purification.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
APPLIED SURFACE SCIENCE
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2025
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IF 6.9
Quanxiao Deng,Dezhong Song,Youzhen Liu,Ruizhi Yin,Chunyan Liu,Jia Huo
Carbon-based single-atom catalysts have demonstrated excellent performance in electrochemical CO 2 reduction reactions. However, the traditional planar, highly symmetric MN 4 structures seriously restrict their activities due to relatively weak interactions between the catalyst and CO 2 . In this work, we demonstrated a novel and controllable method for axial P coordination of single-atom Ni catalyst through low-temperature post-functionalization. This modification significantly regulates the spin state of the Ni sites, thereby increasing the interaction between CO 2 and the active sites. The axially P-coordinated single-atom Ni catalyst exhibits markedly improved performance for CO 2 conversion to CO, achieving a maximum CO Faradaic efficiency of ∼ 99 % at −0.98 V (vs. RHE) and a partial current density for CO of −45.1 mA cm −2 at −1.48 V (vs. RHE), which is 18.4 % higher than that of the pristine single-atom Ni catalyst. Density functional theory calculations indicate that axial P coordination modulates the magnetic moment of the Ni active center and the 3d orbital splitting energy levels, thereby promoting CO 2 adsorption and facilitating CO desorption by optimizing the binding energies of reaction intermediates. These findings are confirmed by experimental electron spin resonance measurements. This work provides a facile strategy for regulating the electronic structures of single-atom catalysts and highlights the potential for spin-state modulation to significantly enhance CO 2 electroreduction.
研究领域:
材料科学
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电化学
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理论计算
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产品关联
DOI
高影响因子
Journal of Energy Chemistry
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2024
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IF 14
Yugang Qi,Qing Liang,Kexin Song,Xinyan Zhou,Meiqi Liu,Wenwen Li,Fuxi Liu,Zhou Jiang,Xu Zou,Zhongjun Chen,Wei Zhang,Weitao Zheng
Atom-level modulation of the coordination environment for single-atom catalysts (SACs) is considered as an effective strategy for elevating the catalytic performance. For the MN x site, breaking the symmetrical geometry and charge distribution by introducing relatively weak electronegative atoms into the first/second shell is an efficient way, but it remains challenging for elucidating the underlying mechanism of interaction. Herein, a practical strategy was reported to rationally design single cobalt atoms coordinated with both phosphorus and nitrogen atoms in a hierarchically porous carbon derived from metal-organic frameworks. X-ray absorption spectrum reveals that atomically dispersed Co sites are coordinated with four N atoms in the first shell and varying numbers of P atoms in the second shell (denoted as Co-N/P-C). The prepared catalyst exhibits excellent oxygen reduction reaction (ORR) activity as well as zinc-air battery performance. The introduction of P atoms in the Co-SACs weakens the interaction between Co and N, significantly promoting the adsorption process of *OOH, resulting in the acceleration of reaction kinetics and reduction of thermodynamic barrier, responsible for the increased intrinsic activity. Our discovery provides insights into an ultimate design of single-atom catalysts with adjustable electrocatalytic activities for efficient electrochemical energy conversion.
研究领域:
材料科学
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电化学
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催化科学
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产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2024
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IF 13.3
Luming Wang,Guoliang Zhang,Hui Zhao,Gang Wang,Zengxi Li,Chunshan Li
Recently, the development of separable and recycling heterogeneous catalyst for ethylene hydroesterification to methyl propionate (MP) has attracted wide interest of researchers. Herein, a kind of 1, 2-bis(di- tert -butyl phosphinomethyl)benzene (dtbpb)-functionalized hypercrosslinked polymers (HCPs) coordinated with Pd single-atom sites was designed and utilized for heterogeneous hydroesterification of ethylene to MP using CO and methanol. The as-prepared catalyst series were characterized with FT-IR, SEM, XPS, NMR, HRTEM, HAADF-STEM, and XAS, which confirmed the coordination structure of Pd with dtbpb ligand linked to HCPs, as well as the dispersion of Pd in the form of single atoms on the polymer support. The effects of Pd loading and reaction conditions on the ethylene hydroesterification were systematically investigated. As a result, 100 % selectivity of MP with 96.2 % conversion of ethylene were achieved on Pd/dtbpb@HCPs catalyst under the optimal condition and no obvious deactivation behavior was observed during the recycling evaluation. The detailed reaction mechanism of ethylene hydroesterification was proposed by identification of crucial intermediates of Pd-H, Pd-alkyl and Pd-acyl species by employing in-situ DRIFTS. The kinetic study was conducted and the reaction orders of ethylene and CO are corresponding to 0 and 0.5, with the activation energy of 50.7 kJ/mol.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
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IF 19
Xing Lai,Weiye Xu,Yukui Gou,Hongxiang Zhang,Jianying Huang,Weilong Cai,Yuekun Lai
Phytate (PhA) holds considerable promise for constructing molecular sieve membranes due to its high density of long-range electrostatic attractions, customizable charge density, and excellent polymer affinity. Herein, PhA-Fe 3+ complexes constructed by controllable coordination assembly are presented, based on metal-organophosphorus biphasic interfacial coordination reactions, and use the PhA-Fe 3+ complexes to regulate the interfacial polymerization (IP) process to generate polyamide (PA) nanofiltration membranes. The PhA-Fe 3+ complexes impart a high density of long-range electrostatic and short-range hydrogen bonding forces to the amine monomers and provide tunable charge densities through flexible metal-organophosphate coordination. Hydrogen bonding and strong electrostatic interactions spatially enrich the amine monomers and temporally slow down their diffusion into the hexane phase, as demonstrated by molecular simulations, resulting in a PA/PhA-Fe 3+ membrane with increased surface area, enhanced microporosity, lower thickness, higher water density near pores, and nanoscale spotted structures. Those structures are recognized as the key factor in achieving a water permeance of 19.2 L m −2 h −1 bar −1 , alongside a MgCl 2 rejection of 96.7% and a Li + /Mg 2+ selectivity of 24.1 (Mg 2+ /Li + mass ratio = 20), surpassing those of reported nanofiltration membranes. This PhA-Fe 3+ complexes-modulated IP strategy offers fresh perspectives for constructing a highly permeable membrane for lithium extraction from salt lake brines. Graphical Here, PhA-Fe 3+ complexes are synthesized through metal-organophosphorus biphasic interfacial coordination to modulate interfacial polymerization, yielding polyamide nanofiltration membranes. Molecular simulations confirm that hydrogen bonding and electrostatic interactions spatially confine amine monomers while retarding their diffusion into hexane, endowing such ultrathin PA/PhA-Fe 3+ membrane with enhanced microporosity, enlarged surface area, nanoscale spotted morphology, and optimized hydration layer density at the pore interfaces. The optimized membrane exhibits high permeability and stable Li + /Mg 2+ selectivity.
研究领域:
膜科学
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材料工程
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电化学
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化学分离
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纳米技术
✓ 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）