ACS Sustainable Chemistry & Engineering
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2025
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IF 7.3
Ranran Wei,Xiaoying Zhang,Min Yan,Yaxuan Li,Ruichen Geng,Zekai Shen,Yinglong Wang,Shuli Yin
Ammonia (NH3), the second most produced chemical in the world, is predominantly utilized in fertilizer production to underpin modern agriculture and has recently attracted interest as an energy-dense source of renewable energy. Herein, an amorphous CuTe porous nanonets (CuTe PNs) catalyst with p-d orbital hybridization was designed and prepared for NH3 synthesis via the nitrite reduction reaction. The porous and amorphous structure of CuTe PNs provides sufficient channels for molecular penetration and enhances active site accessibility through its abundant defects and vacancies, facilitating electrochemical reactions. The CuTe PNs exhibit excellent nitrite reduction reaction performance (NH3 yield: 633.7 μg h–1 mgcat–1, Faradaic efficiency: 91.41%, NH3 selectivity: 92.2%). This work describes a powerful pathway for the fabrication of p-d orbital hybrid amorphous porous nanonets catalysts and also provides a new possibility for the electrochemical synthesis of NH3.
研究领域:
材料科学
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电化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
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2025
·
IF 19
Xinyu Wang,Sichen Huo,Yanjie Chen,Mingyi Wang,Ying Dai,Jinlong Zou
Cobalt atom cluster (Co AC )-based electrocatalysts usually exhibit high activity for oxygen reduction reaction (ORR), but display limited performance in oxygen evolution reaction (OER). To enhance their bifunctional catalytic efficiency, it is crucial to tailor the d -orbital electronic structure of Co AC through orbital coupling effect, optimizing the chemisorption of O-intermediates. Herein, a 3 d -4 d orbital coupling strategy is used to construct a Co AC -molybdenum carbide/nanocarbon cake (Co AC -Mo x C/CC) catalyst with a hollow structure for ORR/OER in zinc-air batteries (ZABs). Experimental and theoretical results confirm that the 4 d transition metal Mo, with fewer d electrons and more unfilled orbitals, interacts strongly with Co sites through d - d coupling, promoting electron enrichment and triggering 3 d -orbital electron delocalization. This process accelerates the rate-limiting steps of *OH desorption for ORR and *OOH formation for OER, leading to an ultra-low potential gap of 0.604 V and improved stability. Notably, the Co AC -Mo x C/CC-based liquid and flexible all-solid-state ZABs exhibit excellent performance with high open-circuit voltages of 1.49 and 1.47 V, and power densities of 146.4 and 103.4 mW cm −2 , respectively, highlighting their potential to replace precious metal catalysts. This study may open new avenues for manipulating the electronic properties of Co AC -based electrocatalysts and boosting activity through the d - d orbital coupling strategy.
研究领域:
材料科学
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电化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2016
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IF 7.145
Meilin Lv,Gang Liu,Xiaoxiang Xu
Strong visible light absorption and high charge mobility are desirable properties for an efficient photocatalyst, yet they are hard to be realized simultaneously in a single semiconductor compound. In this work, we demonstrate that these properties coexist in homologous compounds ZnnIn2O3+n (n = 4, 5, and 7) with a peculiar layered structure that combines optical active segment and electrical conductive segment together. Their enhanced visible light absorption originates from tetrahedrally or trigonal-bipyramidally coordinated In atoms in Zn(In)O4(5) layers which enable p–d hybridization between In 4d and O 2p orbitals so that valence band minimum (VBM) is uplifted with a reduced band gap. Theoretical calculations reveal their anisotropic features in charge transport and functionality of different constituent segments, i.e., Zn(In)O4(5) layers and InO6 layers as being for charge generation and charge collection, respectively. Efficient photocatalytic hydrogen evolution was observed in these compounds under full range (λ ≥ 250 nm) and visible light irradiation (λ ≥ 420 nm). High apparent quantum efficiency ∼2.79% was achieved for Zn4In2O7 under full range irradiation, which is almost 5-fold higher than their parent oxides ZnO and In2O3. Such superior photocatalytic activities of these homologous compounds can be understood as layer-by-layer packing of charge generation/collection functional groups that ensures efficient photocatalytic reactions.
研究领域:
材料化学
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光催化
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半导体物理
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能源材料
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无机化学
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表面科学
✓ 已验证
DOI
高影响因子
Inorganic Chemistry Frontiers
·
2025
·
IF 6.4
Ruichen Geng,Lin Su,Xiaojun Chu,Zhihan Zhang,Ranran Wei,Yinglong Wang,Shuli Yin
Developing electrocatalysts with high activity and selectivity to promote the oxidation of 5-hydroxymethylfurfural (HMF) holds substantial importance yet presents challenges in the realm of biomass upgrading. Herein, the defect-rich high-entropy alloy AuCuAgRuNi nanofibers (AuCuAgRuNi NFs) were synthesized via a facile one-pot wet chemical synthesis. Remarkably, the AuCuAgRuNi NFs demonstrate exceptional electrocatalytic performance for HMF-to-FDCA conversion under ambient conditions, achieving 97.15% yield and 98.40% selectivity with outstanding stability. Theoretical calculations reveal that defect-induced electronic modulation optimizes reactant adsorption, while d-orbital hybridization among multi-metallic components facilitates electron redistribution, synergistically enhancing catalytic activity. Furthermore, HMF oxidation has been successfully integrated with hydrogen evolution in a flow electrolysis cell, and an energy-efficient coupled system has been established, which holds promise for scalable biomass valorization. This research provides valuable insights into the innovative synthesis and inherent catalytic mechanisms of high-entropy alloy systems.
研究领域:
催化化学
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纳米技术
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电化学
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材料科学
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生物质转化
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理论化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Zizai Ma,Zihao Wan,Shuaili Zhao,Jinping Li,Jianping Du,Xiaoguang Wang
Bimetallic single-atom catalysts have garnered considerable interest in the field of the oxygen reduction reaction due to their unique electronic configurations and synergistic catalytic effects. However, precise modulation of d-orbital electron distribution at single-atom sites and comprehensive elucidation of the underlying catalytic mechanisms continue to present significant challenges. Herein, the FeCo(mlm)–N–C catalyst, integrating atomically dispersed Fe–Co dual-metal sites and Fe3C nanoparticles, was synthesized by using an encapsulation and ligand exchange strategy. Comprehensive analyses and theoretical simulations reveal that the incorporation of Fe3C nanoparticles induces significant d-orbital electron delocalization at the Fe active sites. This tailored electronic configuration effectively modulates Fe d–O p hybridization between the Fe active sites and adsorbed OH*. Consequently, it optimizes the occupancies of bonding and antibonding orbitals, thereby accelerating OH* desorption. This mechanism enables FeCo(mlm)–N–C to exhibit excellent catalytic performance and remarkable stability in both acidic and alkaline environments, while demonstrating superior activity in zinc-air batteries and proton exchange membrane fuel cells. This work not only presents a highly efficient non-noble metal electrocatalyst but also provides valuable insights into the rational development of advanced transition metal–nitrogen–carbon catalysts for energy-related applications.
研究领域:
电化学
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催化
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材料科学
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纳米技术
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能量转换
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Huan Chen,Yan Zhao,Zhe Zhang,Bo Niu,Yayun Zhang,Donghui Long
In this work, a cobalt phthalocyanine catalyst with axial pyridine coordination anchored on carbon nanotubes (CoPc-Py-CNT) was developed for enhanced peroxymonosulfate (PMS) activation toward singlet oxygen ( 1 O 2 ) evolution. Axial pyridine coordination induces Co 3 d -N 2 p rehybridization, elevating the Co d z 2 orbital energy level to strengthens d-p orbital hybridization with the oxygen atom in PMS, thereby lowering the activation energy barrier for O-O bond cleavage. The CoPc-Py-CNT/PMS system exhibits an 8.3-fold increase in ciprofloxacin degradation rate and nearly quantitative selectivity in aromatic alcohol oxidation to corresponding aldehydes compared to axially unmodified CoPc-CNT. CoPc-Py-CNT maintains excellent performance in both continuous-flow and 50 L pilot-scale water treatment systems, with minimal cobalt leaching (<20 μg L −1 ) and negligible ecotoxicity. This work proposes a tailored symmetry-breaking strategy via axial coordination to modulate the electronic structure of SACs, offering a robust platform for 1 O 2 -mediated water remediation and selective oxidation reactions in green chemistry applications.
研究领域:
环境化学
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催化
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材料科学
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水处理
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绿色化学
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配位化学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED MATERIALS
·
2025
·
IF 26.8
Jing Zhang,Peiqi Shen,Yuchun Liu,Tianchen Wei,Xingwu Zhai,Baichuan Zhu,Jianrong Zeng,Kun Xu,Min Zhou
Lithium carbonate, the primary discharge product in Li–CO 2 batteries with high thermodynamic stability and a wide band gap, leads to significant electrochemical inertness, limiting efficiency and cycle life. The strongly delocalized p z orbital at a lower-energy HOMO level in Li 2 CO 3 causes weak coupling with the O-p z orbitals, increasing decomposition resistance owing to d-orbital degeneracy in high-local-symmetry catalysts. This study introduces metastable tetragonal-pyramidal nickel sulfide (tp-NiS) with low-symmetry NiS 5 coordination, breaking d-orbital degeneracy and bringing d z 2 , d xz , and d yz orbitals closer to the Fermi level. Enhanced orbital overlap with Li 2 CO 3 O-p z orbitals facilitates robust Ni–O bond formation. In situ spectroscopy confirms reversible Ni–O bond formation during cycling, ensuring electron transfer and complete Li 2 CO 3 decomposition. Conversely, weak interfacial interactions in octahedral NiS with highly symmetric local coordination only allow decomposition-resistant Li 2 CO 3 and interface passivation. Consequently, tp-NiS exhibits superior electrochemical performance, with the best reported reversibility and stability, a charge potential below 4.0 V, and 92.03% capacity retention after 1800 h. This metal redox-driven mechanism establishes a reversible geometric conversion pathway, emphasizing the critical role of symmetry-engineered Ni–O interactions in bifunctional catalysts.
研究领域:
电化学
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材料科学
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储能
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催化
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电池技术
✓ 已验证
产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）