Nature Communications
·
2025
·Vol. 16
·期 1
·1-11
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IF 15.7
Long Haoyu,Zhang Xidong,Zhang Zhenyi,Zhang Jianjun,Yu Jiaguo,Yu Huogen
The H 2 -evolution kinetics play a pivotal role in governing the photocatalytic hydrogen-evolution process. However, achieving precise regulation of the H-adsorption and H-desorption equilibrium (H ads /H des ) still remains a great challenge. Herein, we propose a fine-tuning d - p hybridization strategy to precisely optimize the H ads /H des kinetics in a Ni-B x modified CdS photocatalyst (Ni-B x /CdS). X-ray absorption fine-structure spectroscopy and theoretical calculations reveal that increasing B-atom amount in the Ni-B x cocatalyst gradually strengthens the d - p orbital interaction between Ni 3 d and B 2 p , resulting in a consecutive d -band broadening and controllable d -band center on Ni active sites. The above consecutive d -band optimization allows for precise modulation of the H ads /H des dynamics in the Ni-B x /CdS, ultimately demonstrating a remarkable H 2 -evolution activity of 13.4 mmol g -1 h -1 (AQE = 56.1 %). The femtosecond transient absorption spectroscopy further confirms the rapid electron-transfer dynamics in the Ni-B x /CdS photocatalyst. This work provides insights into the optimal design of prospective H 2 -evolution catalysts.
研究领域:
材料科学
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催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano-Micro Letters
·
2023
·Vol. 16
·期 1
·1-18
·
IF 26.6
Li Xudong,Qiang Zhuomin,Han Guokang,Guan Shuyun,Zhao Yang,Lou Shuaifeng,Zhu Yongming
High-entropy catalysts featuring exceptional properties are, in no doubt, playing an increasingly significant role in aprotic lithium-oxygen batteries. Despite extensive effort devoted to tracing the origin of their unparalleled performance, the relationships between multiple active sites and reaction intermediates are still obscure. Here, enlightened by theoretical screening, we tailor a high-entropy perovskite fluoride (KCoMnNiMgZnF 3 -HEC) with various active sites to overcome the limitations of conventional catalysts in redox process. The entropy effect modulates the d -band center and d orbital occupancy of active centers, which optimizes the d – p hybridization between catalytic sites and key intermediates, enabling a moderate adsorption of LiO 2 and thus reinforcing the reaction kinetics. As a result, the Li–O 2 battery with KCoMnNiMgZnF 3 -HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability, preceding majority of traditional catalysts reported. These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·Vol. 34
·期 29
·2316448
·
IF 18.5
Zhihua Zhang,Yangyu Zhu,Xiaoyue Shi,Baotong Qi,Yu Ding,Yan Du,Wanfeng Shi,Jian Zhang,Jian Liu,Yuanhua Sang,Zeyan Wang,Lei Zhang,Haohai Yu,Huaijin Zhang,Bin Cai,Mingwen Zhao,Yangyang Li
Orbital degree of freedom plays a crucial role in governing the physical and chemical properties of solid materials, and it is widely investigated in the fields of physics, material science, and chemistry. Typically, orbital-energy-related scenarios, such as d-band center or electron occupancy, have been discussed in the catalytic materials, since they can control the surface-adsorbate bonding strength to modulate the catalytic activity. However, the impact of orbital morphology, that is the “posture” of orbitals on catalysts' surfaces, has never been studied. Here the importance of 3 d -orbital morphology on the activity of oxygen reduction reaction (ORR) in a strongly correlated oxide α-Ti 2 O 3 is highlighted. Superior ORR performance is observed in α-Ti 2 O 3 (Ti 3+ :3 d 1 ) than that of the anatase and rutile TiO 2 (Ti 4+ :3 d 0 ), with higher Faradaic efficiency (87.3%) and H 2 O 2 selectivity (93.2%). More importantly, a novel orbital-morphology-based mechanism is developed and the orbital morphology dominates the catalytic activity by determining the surface-adsorbates d – p orbital hybridization via orbitals' overlap, resulting in a crystal-plane-dependent ORR activity in α-Ti 2 O 3 . The work reveals the strong interplay between the orbital morphology, d – p hybridization, and ORR activity, which broadens the fundamental understanding of catalysts from a new view of the orbital degree of freedom.
研究领域:
材料科学
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化学
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物理学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2024
·
IF 9.4
Xiaofei Zhou,Guijuan Wei,Chang Liu,Qian Zhao,Hui Gao,Wenbo Wang,Xixia Zhao,Xin Zhao,Honglei Chen
The production of hydrogen through seawater electrolysis has recently garnered increasing concern. However, hydrogen evolution reaction (HER) by alkaline seawater electrocatalysis is severely impeded by the slow H 2 O adsorption and H* binding kinetics at industrial current densities . Herein, a face-centered cubic/hexagonal close packed (fcc/hcp) NiRu alloy heterojunction was fabricated on Ni foam (N doped NiRu-inf/NF) by a low-temperature nitrogen plasma activation. Simultaneously, nitrogen atoms are introduced into the alloy to facilitate d-p hybridization. When N doped NiRu-inf/NF is integrated into a dual-electrode cell for urea-assisted seawater electrolysis, it achieves 100 mA cm −2 with an ultra-low voltage of 1.36 V and excellent stability. Density functional theory (DFT) verifies that the robust d-p hybridization among Ni, Ru and N exhibits more energy level matching for H 2 O molecule adsorption at the Ru sites, while simultaneously reducing the interaction between H* and Ni sites in N -doped NiRu-inf.
研究领域:
材料科学
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电化学
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能源材料
·
催化
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）