ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Lanlan Yu,Jincheng Mu,Huiling Liu,Gang Liao,Boyi Li,Yufen Xia,Zhimin Wang,Jili Yuan,Jiachao Shen,Chengbin Liu
Electrocatalytic nitrate reduction into ammonia (NitRR) over Co-based catalysts is attractive but still constrained by the competition with H* coupling to produce H 2 . Additionally, the fundamental mechanism underlying the interfacial engineering associated with electronic state transformation for strengthening oriented NitRR remains elusive. Herein, a Co(OH) 2 /Bi 12 O 17 Br 2 heterostructure is fabricated using a one-step wet chemistry method, performing remarkable reactivity for NH 3 production own to the formation of electron-deficiency Co sites induced by Bi 12 O 17 Br 2 . Unexpectedly, the NitRR activity of Co(OH) 2 /Bi 12 O 17 Br 2 increases gradually in the initial stage and then keeps at a high level, which is uncovered as the reconstruction of Bi 12 O 17 Br 2 into Bi 0 . Theoretical calculations suggest that the in situ reconstruction guides the electron-deficiency of Co and the shift of d -band center of Co toward the Fermi level, thus promoting the adsorption and conversion of intermediates. The synergistic effect of the hydrolysis dissociation over Co(OH) 2 and the inhibition of H* coupling over Bi 0 contributes to high selectivity and activity for NitRR. The reconstructed catalyst shows a high ammonia yield rate of 7343.3 µg h −1 mg −1 at −0.6 V versus RHE and nearly 100% Faradaic efficiency at −0.4 V versus RHE. This study provides insight into the strengthening mechanism of Co-based catalysts for NitRR.
研究领域:
电催化
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材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Science Bulletin
·
2025
·
IF 21.1
Mingxia Zhang,Jiahui Peng,Zhong Zhang,Xujiao Ma,Songzhu Xing,Yiwei Liu
The strategic introduction of defects in polyoxometalate-based metal–organic frameworks (POM@MOFs) enables synergistic catalytic effects between POMs and defect sites, achieving catalytic functions unattainable by either component alone. However, the complexity of the POM@MOFs synthetic system makes the controlled construction of defects more challenging than in conventional MOFs. Herein, we develop an atomic substitution-modulated host-guest interaction strategy for controlled synthesis of electron-deficient defect sites in POM@MOFs with tunable missing-linker content. Specifically, the gradual substitution of Mo atoms with V atoms in H 3 PMo 12 O 40 (PMo 12 ) enhances the nucleophilicity of surface oxygen species, thereby strengthening the interaction between POMs and Zr 6 -oxo clusters in UiO-67. This enhanced interaction induces varying degrees of ligand loss through coordination competition of POMs with organic ligands during the self-assembly of POM@UiO-67. Meanwhile, POMs acting as electron sponges withdraw electrons from UiO-67, resulting in lower electron density at defect sites compared to traditional defective UiO-67. The induced defect sites exhibit superior catalytic performance in the transfer hydrogenation of cinnamaldehyde, due to a significantly reduced hydrogen transfer energy barrier. This work provides a new perspective for designing crystalline porous catalysts with synergistic effects based on the modulation of host-guest interaction.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
Zhang Shi-Nan,Gao Peng,Liu Qian-Yu,Zhang Zhao,Leng Bing-Liang,Chen Jie-Sheng,Li Xin-Hao
Electrochemical nitrate reduction reaction offers a sustainable and efficient pathway for ammonia synthesis. Maintaining satisfactory Faradaic efficiency for long-term nitrate reduction under ampere-level current density remains challenging due to the inevitable hydrogen evolution, particularly in pure nitrate solutions. Herein, we present the application of electron deficiency of Ru metals to boost the repelling effect of counter K + ions via the electric-field-dependent synergy of interfacial water and cations, and thus largely promote nitrate reduction reaction with a high yield and well-maintained Faradaic efficiency under ampere-level current density. The pronounced electron deficiency of Ru metals boosts the repelling effect on hydrated K + ions, as indicated by the distance of K + ions to catalyst surface, which can loosen the water layer to depress hydrogen evolution and accelerate nitrate conversion. Consequently, the optimized electrode loaded with electron-deficient Ru atomic layers can directly produce 0.26 M ammonia solution in pure nitrate solution in 6 h, providing a high yield (74.8 mg mg cat –1 h –1 ) and well-maintained the Faradaic efficiency for over 120 h under ampere-level reduction.
研究领域:
电化学
·
催化材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Nano Energy
·
2018
·
IF 13.12
Peng Zhou,Fan Lv,Na Li,Yelong Zhang,Zijie Mu,Yonghua Tang,Jianping Lai,Yuguang Chao,Mingchuan Luo,Fei Lin,Jinhui Zhou,Dong Su,Shaojun Guo
Tuning reactive metal-support interaction (RMSI) is a promising approach to optimizing catalytic active sites via the electronic, geometric and compositional effects. In general, the RMSI is conducted on the reducible oxides via a high-temperature reaction (>550 °C). Herein we report a strong RMSI between Pt single atom (PtSA) and non-oxide-based g -C 3 N 4 built by an in-situ photocatalytic reduction method at a sub-zero temperature. The experimental observation confirms that the rich N vacancies in g -C 3 N 4 produce an obvious electron-deficient effect, which greatly enhances the RMSI. This strong RMSI contributes to the highest PtSA coverage density of 0.35 mg m −2 reported to date in carbon-based materials and outstanding H 2 -evolution activity of 174.5 mmol g −1 h −1 per PtSA relative to those on the electron-rich g -C 3 N 4 . The structure simulation reveals that the RMSI can not only stabilize the PtSA on the electron-deficient g -C 3 N 4 via the strong chemical bond between PtSA and the two-coordinated C (C 2C ) sites caused by the N vacancies, but also promises the PtSA with an optimized electronic and geometric structures for capturing photogenerated electrons and producing H 2 . This finding opens a new channel for designing and manipulating single atom-loaded photocatalyst via the RMSI at a sub-zero low temperature.
研究领域:
材料科学
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催化化学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
Catalysis Science & Technology
·
2015
·Vol. 6
·期 6
·1913-1920
·
IF 5.426
Renfeng Nie,Hezhan Jiang,Xinhuan Lu,Dan Zhou,Qinghua Xia
N-doped active carbon (N-AC) has been synthesized via heat treatment of a mixture consisting of dicyandiamide as the nitrogen source and commercial active carbon as the precursor. This material is especially adapted for anchoring ultrafine Pd nanoparticles by a very clean strategy using H2 as the reductant. The physicochemical properties of materials were investigated by powder X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). The results reveal that the variation of the treatment temperature can assist the tuning of the content of N and the dispersion of Pd on xN-AC, by which Pd nanoparticles with a narrow size distribution centered at around 1.8 nm can be obtained. These robust catalysts show very high catalytic activity for the aromatic ring hydrogenation of acidic substrates, such as electron-deficient benzoic acid or electron-rich phenol, under mild conditions in aqueous media. Excellent catalytic results (9.2 times higher activity in comparison to non-doped catalyst for benzoic acid hydrogenation), high stability and easy recyclability of the catalyst were achieved. The strong interaction between the pyridinic nitrogen group and Pd species will lower the reducibility of the Pd species and result in the formation of relatively electron-deficient and ultra-small sized Pd clusters, thus leading to high hydrogenation activity.
研究领域:
材料化学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
TETRAHEDRON
·
2015
·
IF 2.641
Xingzhu Xu,Haibo Wu,Zhengyi Li,Xiaoqiang Sun,Zhiming Wang
The development of bimetallic iron oxide-silver magnetic nanoparticles (Fe 2 O 3 –Ag MNPs) catalytic system provides an efficient heterogeneous synthetic pathway to allylic amines and 1,2-dihydroquinolines involving the direct inter/intramolecular nucleophilic substitution of π-activated alcohols with electron-deficient amines. The major advantages of the present method are wide substrate scope, simple product separation, low catalyst loading, and magnetically recyclable catalyst.
研究领域:
化学
·
材料科学
·
有机合成
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2024
·Vol. 15
·期 47
·4835-4841
·
IF 4.1
Yiyang Xiao,Zepeng Zhang,Yan Xu,Jianbo Wang
Here, α-styrylboronic acid pinacol ester (StBpin) has been found to undergo alternating radical copolymerization with electron-deficient olefin comonomers, including n-butyl acrylate, N,N-dimethylacrylamide, acrylonitrile, and N-ethylmaleimide. Compared with styrene, which also copolymerizes with these electron-deficient olefins in an alternating manner, StBpin resulted in the formation of copolymers with higher alternating selectivity, but lower yields and low molecular weights due to its diminished reactivity.
研究领域:
高分子化学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CATALYSIS TODAY
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2020
·
IF 5.825
Juan Liu,Wen-Ying Li,Jie Feng,Xiang Gao
The improvement of the sulfur tolerance over Pt catalyst is critical for the hydrotreatment of crude oil. Fe was co‒impregnation with Pt on γ-Al 2 O 3 at different calcination temperature. Results revealed that adding Fe significantly facilitated the reduction of Pt oxides for the catalyst calcined at 400 °C. The morphological analysis and CO chemisorption showed Fe improved the dispersion of Pt nanoparticles. The surface chemical state analysis implied the co‒existence of the electron‒deficient Pt and metallic Fe. However, the increase of calcination temperature caused a decreased reducibility of Pt oxides due to strong metal support interaction. A higher dibenzothiophene hydrodesulfurization conversion of 97.7 % with a dominant biphenyl selectivity of 96.7 % were acquired for the catalysts incorporated with Fe. The density functional theory calculations confirmed the alloyed Fe led to the formation of electron‒deficient Pt atoms, and the higher affinity to sulfur made Fe be a favorable additive for noble metal catalyst in the hydrodesulfurization.
研究领域:
催化
·
化工
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
·
2025
·
IF 2.9
Xinyu Lu,Zongyou Cao,Yiping Mo,Wenjing Zhang,Danyang Zhu,Baolong Liu,Wangyang Lu
Covalent organic polymers (COPs) are considered promising non-precious metal catalysts for ORRs. However, as bulk COP powder generally suffers from poor electrical conductivity, heat treatment is frequently performed after the reaction, which inevitably destroys their originally designed regular structure, making their active sites complex and uncontrollable. Herein, we successfully prepared a novel naphthalene diimide-based bimetallic phthalocyanine covalent organic polymers@carbon nanotube nanocomposite electrocatalyst (CoFe/NDI-COP@CNT) via a simple solvothermal method. The non-pyrolytic preparation method greatly preserves the ordered structure of the COP framework and the well-defined active sites (CoN4 and FeN4). Moreover, incorporating an electron-poor NDI component into the target grid skeletons can increase the hybrid catalyst's ability to accept electrons from oxygen and further increase the density of active sites. Under the alkaline condition of 0.1 M KOH, CoFe/NDI-COP@CNTs exhibit efficient ORR catalytic activity and stability, with a half-wave potential of 0.902 V and a limiting current density of 5.362 mA cm−2, which is superior to that of 20% Pt/C. In addition, CoFe/NDI-COP@CNTs show exceptional methanol resistance and electrochemical stability. This work provides new insights for the non-pyrolysis preparation of metal-doped carbon electrocatalysts with well-defined active sites from COPs.
研究领域:
材料科学
·
电化学
·
纳米技术
·
高分子化学
·
催化
✓ 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）