ACS Catalysis
·
2025
·
IF 13.1
Yi Zhang,Habib Ullah,Linfeng Li,Hsiao-Chien Chen,Xia Zhang,Qiangli Lv,Xuefei Xu,Shaowei Zhang,Chao Hu,Zhishan Li,Muhammad Humayun,Mohamed Bououdina,Hussein A. Younus,Deli Wang,Chundong Wang
The design and development of highly efficient, stable, and low-cost electrocatalysts for the oxygen evolution reaction (OER) is crucial for green hydrogen production. Metal–organic frameworks (MOFs), with the merits of structural diversity and tunable organic ligand nature, have significant potential. Herein, a Co-based MOF (CoMnFcMOF) electrocatalyst was fabricated under hydrothermal conditions using Mn as a dopant and a ferrocene-based dicarboxylate linker. The as-prepared CoMnFcMOF enables a current density of 100 mA·cm–2 with an overpotential of 238 mV under an alkaline condition. The well-addressed OER activity is attributed to the spin state modulation of Co induced by Mn incorporation, as verified experimentally and from density functional theory calculations. The total effective magnetic moment (μeff) considerably decreases from 3.992 μB/f.u. in CoFcMOF to 1.974 μB/f.u. in CoMnFcMOF, indicating a spin transition from a high spin (HS) to an intermediate spin (IS) state. This spin modulation facilitates the adsorption of the O* intermediates, thereby accelerating the reaction kinetics. This work establishes a design paradigm for high-performance transition metal-based catalysts through spin state engineering.
研究领域:
材料化学
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电催化
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无机化学
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能源化学
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物理化学
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纳米材料
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可持续能源技术
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Zhangtao Liu,Shuhan Fu,Yuhui Wang,Zhenyang Xu,Yueguang Chen,Ning Xiao,Shangyi Li,Tingting Zhang
A novel spin-state engineering strategy was developed via La doping to break the “oxo wall” and boost high-valent Co(IV)=O generation for efficient per- and polyfluoroalkyl substances (PFASs) degradation. This was achieved by constructing unsaturated CoO 3 single atoms anchored on La-doped MCM-48 (CoLa@MCM-48) via one-pot synthesis, which enabled synergistic activation of peroxymonosulfate and ozone. The optimized catalyst achieved 99.5 % degradation of PFASs substitute sodium p-perfluorous nonenoxybenzene sulfonate (OBS) in 30 min, while maintaining robust performance across diverse water matrices. The incorporation of La induces asymmetric lattice strain through its large ionic radius and spin-orbit coupling, transforming the Co coordination geometry from conventional octahedral symmetry to an unsaturated trigonal planar CoO 3 configuration with a high-spin state, thereby enhancing the 88.8 % generation of Co(IV)=O. This work establishes heteroatom-mediated spin-state engineering for designing high-performance non-radical catalysts to remediate recalcitrant pollutants.
研究领域:
环境催化
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材料化学
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污染控制化学
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高级氧化技术
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配位化学
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表面科学
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纳米催化
✓ 已验证
产品关联
DOI
高影响因子
DESALINATION
·
2024
·
IF 8.3
Xueying Gao,Weijie Fu,Yanfei Sun,Shiyu Wang,Zishan Hou,Feike Zhang,Xiaoxuan Wang,Shuyun Yao,Jinrui Wang,Yuanming Liu,Shuyuan Li,Kaiqi Nie,Jiangzhou Xie,Zhiyu Yang,Yi-Ming Yan
Manganese dioxide (MnO 2 ) has been recognized for its high theoretical capacitance. Recent advancements highlight the potential of modulating the spin state of Mn to elevate charge transfer kinetics. Nonetheless, the specific relationship between Mn spin distribution and desalination efficacy, alongside the underlying mechanism, remains elusive. This study introduces the novel concept of half-disturbed spin desalination , elucidating its complex mechanism via the strategic induction of oxygen vacancies on the MnO 2 surface. Theoretical analyses reveal that electron transfer from the O p y (up) and p z (up) to the Mn d z 2 (up) orbitals alters MnO 2 's spin state from a symmetric low spin to an asymmetric high spin configuration . This transition disrupts spin up symmetry, bolstering dynamic processes and diminishing the ion diffusion energy barrier. Consequently, oxygen vacancy-enriched MnO 2 (V O -MnO 2 ) demonstrates an enhanced specific capacitance of 289 F g −1 at 1 A g −1 . Remarkably, in the hybrid capacitive deionization (HCDI) process, it achieves a superior salt adsorption capacity (SAC) of 56.5 mg g −1 and a salt adsorption rate (SAR) of 2.5 mg g −1 min −1 . This research pioneers the correlation between spin desalination mechanisms and spin state applications, paving the way for novel applications across diverse fields.
研究领域:
材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
Crystals
·
2023
·Vol. 13
·期 4
·623
·
IF 2.7
Changzheng Xie,Zhijie Chen,Xinghua Wang,Ying Meng,Yihao Wang
The perovskite LaCoO3and La0.8Sr0.2CoO3thin films were synthesized successfully by a polymer-assisted deposition method. The structural characterization and thermal decomposition measurements indicate that appropriately increasing the annealing temperature is helpful in improving the film crystallinity. Compared with LaCoO3films, the Curie temperature is enhanced to a higher temperature in La0.8Sr0.2CoO3films, which is attributed to the changes in both the valence state and spin state induced by the chemical doping. In addition, a broad transition temperature region is observed in La0.8Sr0.2CoO3films, revealing the existence of inhomogeneous ground states in this system.Keywords:ferromagnetic perovskite;chemical doping;spin-state transition;lattice relaxation
研究领域:
材料科学
·
物理学
✓ 已验证
DOI
高影响因子
iScience
·
2021
·
IF 5.458
Wubin Wu,Baipeng Yin,Wei Peng,Yukun Zhao,Zeyang Zhou,Hua Sheng,Wanhong Ma,Chuang Zhang
The chemical reactions involving excited-state radical pairs (RPs) of parallel/anti-parallel spin configurations are sensitive to magnetic field, leading to the possibilities of magnetically controlled synthesis of chemical compounds. Here we show that the reaction of anthraquinone (AQ) in sodium dodecyl sulfate (SDS) micellar solution under UV excitation is significantly influenced by applying external field. The steady state and time-resolved spectroscopies reveal that the reaction intermediate (pairs of AQH-SDS radicals) can undergo two distinct pathways depending on whether it is spin singlet or triplet, and the field is beneficial to the conversion between spin configurations of RPs. The applied field not only affects the reaction rate constant but also changes the final products. Besides, the aggregation of AQ molecules would change the population of singlets and triplets and thus enhance magnetic field effect. This work represents a promising way of controlling chemical reaction and improving reaction selectivity via magnetic field methods.
研究领域:
物理化学
·
材料科学
✓ 已验证
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Meng Li,Zilong Li,Xiaolong Yu,Yinlong Wu,Cehui Mo,Mi Luo,Ligui Li,Shaoqi Zhou,Qiming Liu,Nan Wang,King Lun Yeung,Shaowei Chen
Development of low-cost, high-performance catalysts for the effective degradation of organic dyes is of both fundamental and technological significance for environmental remediation. Herein, FeN 4 -doped carbon nanotubes exhibit a remarkable catalytic activity towards the degradation of acid orange 7 (AO7) in the presence of peroxymonosulfate (PMS). This is accounted for by the abundant well-dispersed FeN 4 sites and appropriate adsorption energy. Radical quenching experiments and electron paramagnetic resonance measurements suggest that singlet oxygen is the main reactive oxygen species. 57 Fe Mossbauer spectroscopy measurements show that the FeN 4 moieties contain multiple spin states, and in conjunction with density functional theory calculations, confirm that FeN 4 with a low/medium spin state serves as the key sites for PMS activation and hence AO7 degradation. Results from this study highlight the critical role of spin states in FeN 4 in the generation of singlet oxygen for effective degradation of organic pollutants.
研究领域:
环境科学
·
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Tongze Sun,Yansong Liu,Jiage Li,Yanan Zhang,Bowen Zhao,Mingyu Li,Chongjun Zhang,Mingxin Huo,Jingjing Jiang,Shuangshi Dong
Decreasing spin state of cobalt to reduce the redox energy barrier of peroxymonosulfate has been challenging. Herein, we constructed asymmetric coordination of Co−BN 3 to decrease spin state of cobalt from high to medium. The developed medium-spin cobalt-mediated Fenton-like system had a carbamazepine degradation rate constant of 0.815 min −1 and removed 58.0% of chemical oxygen demand, 52% of total phosphorus, 69% of total nitrogen and 85% of ammonia nitrogen from the hospital wastewater. This was attributed to that the medium-spin cobalt formed by the construction of asymmetric Co−BN 3 , enhancing the electrons absorption and donation from dz 2 and dx 2 -dy 2 orbitals to PMS, achieving the reduction in redox energy barrier of peroxymonosulfate for the generation of sulfate radical and singlet oxygen. This work provided a new perspective to develop efficient spin-induced synergistic oxidation Fenton-like water treatment technology.
研究领域:
环境科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Wenlin Zhang,Di Jiao,Lu-Hua Zhang,Fengshou Yu
Iron phthalocyanine (FePc) is a promising non-noble metal catalyst for oxygen reduction reaction (ORR). While, with the plane-symmetric FeN 4 site, the ORR activity of FePc is generally low due to its low ability to adsorb and activate O 2 . Herein, we anchor FePc on Mg(OH) 2 / N -doped carbon nanosheets building the ternary plate-like catalyst FePc/Mg(OH) 2 /NC. Theoretical and experimental results show that due to the formation of FePc/Mg(OH) 2 heterojunction, the electron spin state of the monodisperse iron active site ranges from medium spin (MS, t 2g 5 e g 1 ) to low spin (LS, t 2g 6 e g 0 ), enhancing the adsorption with oxygen-containing intermediates, thereby improving the dynamics of the oxygen reduction reaction. As a result, FePc/Mg(OH) 2 /NC catalyst exhibits an outstanding performance (E 0 = 1.02 V, E 1/2 = 0.91 V) for ORR, superior to the commercial Pt/C electrode (E 0 = 1.01 V, E 1/2 = 0.85 V) and FePc/NC (E 0 = 0.97 V, E 1/2 = 0.87 V) under the alkaline conditions. This work offers a new way for the rational design of effective Fe N C catalysts with the support of metal oxides/hydroxides.
研究领域:
材料科学
·
电化学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2024
·
IF 10.7
Rui-Yuan Li,Yu-Xin Guo,Xiao-Yu Yang,Zhan Liu,Xiaoyun Li,Yu Li,Yiyong Huang,Jinping Liu,Shen Yu,Ming-Hui Sun,Li-Hua Chen,Bao-Lian Su,Yilong Wang
Designing the MoSx-based materials to simultaneously realize high intrinsic activity and reliable stability remains quite challenging since there is a contradictory relationship between them. For example, high intrinsic activity or efficient charge transfer indicates that the MoSx-based materials can provide abundant electron-rich sulfur atoms for hydrogen evolution reaction (HER); lots of H* will attack these sulfur atoms; thus, this results in the massive missing of sulfur atoms and poor electrochemical stability. Instead, electron-deficient sulfur atoms lead to an unsatisfactory HER activity regardless of high stability. Herein, a feasible strategy for spin-state regulation is proposed to promote charge transfer, strengthen the Mo-S bond and activate sulfur atoms of MoSx toward efficient HER. In our strategy, the spin transition of the Co-doped species increases the unpaired electrons, favors wide spin channels and accelerates localized electrons transfer; additionally, Co-doping decreases the band-gap of electrocatalyst. These factors collectively improve charge transfer during HER. Second, the spin- and electronegativity-induced electron redistribution decreases the Mo-S bond length, which efficiently inhibits the massive missing of bridging or apical sulfur atoms. Third, introducing Co species into [Mo3S13]2- nanoclusters activates the terminal sulfur atoms owing to reasonable charge accumulation to favor the absorption of H*. With these benefits, the optimized electrocatalyst demonstrates high intrinsic activity and reliable stability. Our work provides a feasible strategy to design and synthesize the outstanding MoSx-based materials from the spin effect, and presents an insightful understanding of the possible mechanism on hydrogen spillover as well as enhancing their durability and structural stability toward efficient electrocatalysis.
研究领域:
材料科学
·
电催化
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
Chem
·
2022
·
IF 25.832
Xiaoqian Wei,Shaojia Song,Weiwei Cai,Xin Luo,Lei Jiao,Qie Fang,Xiaosi Wang,Nannan Wu,Zhen Luo,Hengjia Wang,Zhihong Zhu,Jing Li,Lirong Zheng,Wenling Gu,Weiyu Song,Shaojun Guo,Chengzhou Zhu
The development of Fe single-atom catalysts is greatly impeded by their lower oxygen reduction reaction (ORR) performance in acid electrolytes when compared with Pt/C catalyst. Herein, we report an unprecedented ORR catalyst consisting of Pd nanoclusters (Pd NC ) and Fe single atoms (Fe–N–C/Pd NC ). Experimental investigations and theoretical calculations indicate that the enhanced ORR activity results from the Pd NC -induced spin-state transition of Fe(II) from low spin to intermediate spin, activating O–O bond through the side-on overlapping and achieving the pathway transition from associative to dissociative process. The over-binding of OH∗ can be facilely released to suppress the site-blocking effect and accelerate the removal of OH∗. In acid conditions, Fe–N–C/Pd NC exhibits excellent ORR performance with impressive half-wave potential (0.87 V), insignificant decay after 30,000 cycles, and a high maximum power density of 920 mW/cm 2 in fuel cell, superior to Pt/C catalyst. This work provides an efficient pathway to design non-Pt catalysts through the spin-regulation strategy.
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
·
2021
·
IF 19.503
Xiangdong Kong,Jingwen Ke,Zhiqiang Wang,Yan Liu,Yibo Wang,Weiran Zhou,Zhengwu Yang,Wensheng Yan,Zhigang Geng,Jie Zeng
A typical mode of CO 2 activation is that d electrons at the d orbital of transition metals transfer to the unoccupied π * orbital of CO 2 . Thus the exploration of the relationship between d -electron behaviors and CO 2 activation is of great importance. Herein, we demonstrate that high-spin state of 3 d electrons in Co 2+ facilitated the activation of CO 2 over Co-salophen-X (X represents to Cl, Br, or I). Among these catalysts, Co-salophen-Br exhibited the highest Faradaic efficiency for CO. Notably, the Faradaic efficiency for CO over Co-salophen-Br reached 98.5 % at −0.70 V versus reversible hydrogen electrode, which was 1.5 and 1.2 times as high as those over Co-salophen-Cl (64.8 %) and Co-salophen-I (81.8 %), respectively. Density functional theory calculations revealed that high-spin state of Co sites decreased the reaction energy barrier for the formation of CO. Based on the analysis of electronic state, the ratio of high-spin state was 65.6 % for Co-salophen-Br, which was the highest among the three Co-based molecules. The Co sites with high-spin state promoted the electron transfer from high-energy 3 d orbital (3 d z2 and 3 d x2-y2 ) of Co to the unoccupied π * orbital of CO 2 , improving catalytic performance.
研究领域:
化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CRYSTAL GROWTH & DESIGN
·
2020
·
IF 4.089
Chang-Yu Meng,Feng Feng Huang,Qin Yao Li,Lei Geng
Introduction of divalent metal oxides into the TeO2 matrix can produce the chemical formula Mn[TemO2m+n] ≡ (MO)n(TeO2)m, compounds in which divalent metal oxides provide oxygen ions to the parent compound TeO2, to cleave neutral Te–O net to form various tellurium(IV) oxide anion [TemO2m+n]2n− and divalent metal cations as balanced charges. [TemO2m+n]2n− can form isolated anion, discrete polyanion, one-dimensional chain and ribbon polyanion, two-dimensional (2D) layered polyanion, and 3D tunnel polyanion depending on the ratio of MO/TeO2. In this work, a new type of inorganic compound AE2[Ni(Te4O10)Cl2] ≡ [(AEO)2(TeO2)4](NiCl2) (AE = Ca, Sr, Ba, Pb) can be obtained by introducing NiCl2 into the compound AE2[Te4O10] ≡ (AEO)2(TeO2)4 (AE = Ca, Sr, Ba, Pb). In AE2[Ni(Te4O10)Cl2] ≡ [(AEO)2(TeO2)4](NiCl2), AEO acts as a structural shearing agent to cleave the neutral Te–O layered structures of parent TeO2 into [Te4O10]4– anionic fragments, and the introduced NiCl2 acts as an “adhesive” to recombine [TemO2m+n]2n− anionic fragments to form new [Ni(Te4O10)Cl2] anionic framework and does not provide additional oxygen ions to cleave the parent compound TeO2. AE2[Ni(Te4O10)Cl2] compounds feature 2D 2∞[Ni(Te4O10)Cl2] anionic layers composed by TeO4E, TeO3+1E (where E is the lone pair of electrons of TeIV) distorted trigonal bipyramid, and NiO4Cl2 octahedra, and the spaces between 2∞[Ni(Te4O10)Cl2] layers are filled with AE2+ cations (acting as charge balance) as well as E (protruding from sides of the layers). The optical band gaps of AE2[Ni(Te4O10)Cl2] (AE = Ca, Sr, Ba, Pb) were evaluated to be ∼3.69 eV through extrapolating the UV–vis–near-infrared optical absorption spectra. Thermogravimetric and differential scanning calorimetry measurements indicate that Ca-, Sr-, Ba-, and Pb-compounds are stable below 787, 716, 648, and 517 °C, respectively, under flowing N2 atmosphere. The effective moments estimated by Curie–Weiss equation show that the Ni2+ cations of AE2[Ni(Te4O10)Cl2] (AE = Ca, Sr, Ba, Pb) are all in high-spin ground states.
研究领域:
无机化学
·
材料科学
✓ 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）