CATALYSIS LETTERS
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2025
·Vol. 155
·期 4
·1-8
·
IF 2.4
Zhang Qian,Li Yuanzheng,Pan Zhengyi,Wang Guang-Hui
Catalytic transfer hydrogenation (CTH) of α , β -unsaturated aldehydes to α , β -unsaturated alcohols over metal oxide catalysts is of potential for industrial application. Herein, we have developed a Ni/f - Al 2 O 3 catalyst comprising atomically dispersed Ni δ + (2 < δ < 3) species on porous leaf-like Al 2 O 3 , over which a > 97% yield of furfuryl alcohol (FOL) from CTH of furfural (FFR) is obtained with a turnover frequency (TOF) of 216 h − 1 . Most importantly, the catalyst can be recycled at least 6 times without obvious loss of activity. Its superior catalytic performance can be attributed to the abundant and stable Ni δ + -type acid-base pairs on the surface of Ni/f - Al 2 O 3 .
研究领域:
化学工程
·
催化科学
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DOI
高影响因子
ACS Catalysis
·
2022
·
IF 13.7
Yafei Li,Boyang Liu,Yu Wang,Shiqing Wang,Xiaocheng Lan,Tiefeng Wang
It is important but challenging to develop non-noble metal catalysts with high activity and selectivity for biomass conversion. The activation of C═O bond is a crucial step in biomass upgradation. Herein, a series of Ni-xP/Al2O3 catalysts with different P/Ni molar ratios were prepared for the conversion of ethyl levulinate to γ-valerolactone. The developed Ni-0.38P/Al2O3 catalyst was 5.4 times more active than conventional Ni/Al2O3 based on turnover frequency and significantly outperformed the state-of-the-art non-noble metal catalysts. The unique catalytic performance was ascribed to the formation of Ni3P phase, which was identified by several characterizations. The results of DFT calculation and characterization by XPS and CO-FTIR revealed that electron was transferred from Ni to P with the formation of Niδ+ sites. In situ FTIR for the surface reaction indicated that Niδ+ acted as a new active site to activate the C═O bond, which rendered the high intrinsic activity of Ni3P for the C═O hydrogenation of EL.
研究领域:
催化
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化学工程
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材料科学
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生物质能源
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DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Yingqiao Zhou,Bowen Yang,Richard L Smith Jr.,Yaqiong Su,Xinhua Qi
The development of recyclable heterogeneous bifunctional catalysts for the efficient conversion of cellulose into high-value platform chemicals is still a significant challenge. Herein, the preparation of carbon-nanosheet-encapsulated nickel phosphide catalysts was performed via solvent evaporation self-assembly and alkali activation, and the as-synthesized catalyst efficiently (3 h) hydrolyzes and hydrogenates microcrystalline cellulose to sorbitol with a sorbitol yield exceeding 90%. As a bifunctional catalyst, nickel phosphide (Niδ+–Pδ–) facilitates the heterolytic cleavage of H2, simultaneously generating in situ acidic Hδ+ species for hydrolysis and hydridic Hδ– species for the hydrogenation of C═O bonds. Unlike conventional catalysts with spatially separated functionalities, this concurrent process avoids intermediate accumulation and side reactions during cellulose conversion. Furthermore, encapsulation by carbon nanosheets suppresses phosphorus leaching under hydrothermal conditions, endowing the catalyst with balanced durability and activity. This work provides fundamental insights into hydrogen activation by transition metal phosphides and advances the design of bifunctional catalysts integrating both acidic and hydrogenation functionalities.
研究领域:
催化
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可再生能源
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生物质转化
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材料科学
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多相催化
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Ye Chen,Xiaokang Sha,Junpo Guo,Xupo Liu,Meinan Chang,Jiayao Qiu,Jingru Zhang,Bowen Cai,Jiashu Tang,Yi Liu,Huaiyu Shao,Deli Wang
Rational design of heteroatom-doped catalysts with prominent reaction kinetics holds immense potential for enhancing biomass electrooxidation processes. Here, we introduce a F-doped NiO nanosheet architecture enriched with F-Ni δ+ -O coordination motifs as an advanced electrocatalyst for the oxidation of 5-hydroxymethylfurfural (HMF). XPS depth profiling and differential charge density calculations reveal that the distinctive F-Ni δ+ -O configuration induces asymmetric charge redistribution at Ni sites, effectively reducing the activation energy for Ni 3+ OOH species and their subsequent interaction with HMF. Meanwhile, pH-dependent and in-situ Raman measurements demonstrate that F sites function as proton relays, facilitating proton transfer and enabling efficient proton-coupled electron transfer kinetics. The synergistic electronic and proton effects endow excellent catalytic performance, with an oxidation current density of 66.45 mA cm −2 and a reaction rate of 5.23 × 10 −4 s −1 , far higher than that of the original NiO. Notably, the catalyst retains over 95 % Faradaic efficiency and yield of 2,5-furandicarboxylic acid (FDCA) after twenty consecutive cycles. This work establishes a dual regulation strategy via heteroatom doping to simultaneously modulate electronic configuration and proton transfer dynamics, offering novel insights into the design of high-performance electrocatalysts for biomass valorization.
研究领域:
电催化
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材料科学
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可再生能源
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可持续化学
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生物质转化
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2026
·
IF 5.1
Zhengyu Zhao,Hongmei Bai,Hongwei Zhang,Qunhong Liu,Hui Guo,Xinru Wu,Kewen Zhang,Di Yang,Qingchen Wu,Cejun Hu,Xiaojun Bao,Pei Yuan
The aqueous-phase hydrogenation of maleic acid (MAc) represents a sustainable approach to succinic acid (SAc) production, yet its efficiency and stability are hampered by the isomerization of MAc to fumaric acid (FAc) and metal leaching under acidic conditions. Herein, we present a nickel phosphide (Ni 3 P) catalyst for the efficient aqueous hydrogenation of MAc. XPS and XAFS analyses reveal the electronic state of the active Ni δ+ species in Ni 3 P is modulated by the annealing temperature. Coupled with adsorption thermodynamics and in situ DRIFTS studies, we demonstrate that a higher density of active sites, an increased surface Ni/P ratio, and electron-enriched Ni δ+ species collectively enhance the adsorption–desorption kinetics of reactants. As a result, the optimized Ni 3 P-400 catalyst achieves complete conversion to SAc with 100% yield and retains full activity over 15 consecutive cycles. These findings underscore the ability of Ni 3 P to tailor the electronic environment of Ni sites, providing a strategy for the design of acid-resistant and high-performance hydrogenation catalysts.
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JOURNAL OF CATALYSIS
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2017
·
IF 6.844
Tingting Hou,Yehong Wang,Jian Zhang,Mingrun Li,Jianmin Lu,Marc Heggen,Carsten Sievers,Feng Wang
In many catalytic processes, metastable reaction intermediates are more valuable and desirable than final products. Here, we report Ni–Ni δ+ clusters on ceria where the extent of reduction of nickel oxide/ceria in H 2 has been optimized. This catalyst shows high selectivity in reducing nitrobenzene to azoxybenzene, the latter usually being metastable. Due to strong electronic metal–support interactions between Ni and ceria, mixed Ni–Ni δ+ clusters are formed on ceria even after reduction at 500 °C in hydrogen. The Ni–Ni δ+ clusters are highly dispersed on ceria, as observed by high-angle annular dark-field scanning–transmission electron microscopy and energy-dispersive X-ray spectroscopy element mapping. This structural uniqueness is clearly reflected in the inhibition of azoxybenzene hydrogenation to aniline, and therefore the catalyst shows high azoxybenzene selectivity (92%). In comparison, the Ni metal catalyst mostly gives aniline and the NiO catalyst has low activity. This study shows how to steer catalytic reactions toward metastable intermediate products by tuning the extent of reduction of metal oxides deposited on reducible oxides.
研究领域:
化学
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催化科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
·
IF 21.1
Shijie Zhang,Dongren Cai,Guifen Du,Weiming Zhu,Jingliu Yang,Xiaoman Wen,Xing Yan,YiKun Zhou,Sajid Ali,Kok Bing Tan,Kang Sun,Guowu Zhan
Regulating product selectivity in CO 2 thermocatalytic hydrogenation remains challenging, particularly for shifting inherent preferences toward C 1 products. Here, we demonstrate that atomic layer deposition (ALD) of ZnO on nickel vanadate precursor (NiVO) enables a dramatic shift from methane (CH 4 ) to carbon monoxide (CO). The optimized NiVO-10ZnO-R400 (10 ALD cycles) achieves 88.1 % CO selectivity at 350°C and 0.1 MPa, surging from 1.3 % over unmodified NiVO-R400. Crucially, ALD-engineered Ni-ZnO interfaces exhibit superior CO production and stability (>200 h) compared to impregnation-synthesized counterparts, attributed to sufficient Ni-ZnO contact. Multimodal characterization and theoretical calculations reveal that ZnO-to-Ni electron transfer generates an electron-rich Ni surface, weakening CO 2 /CO adsorption and lowering surface H concentration. This suppresses the CO→CH 4 step in the CO 2 hydrogenation pathway (CO 2 →CO→CH 4 ), thereby redirecting product selectivity toward CO rather than CH 4 . Our work provides a precise interface-engineering strategy to manipulate reaction pathways for CO 2 utilization.
研究领域:
催化化学
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材料科学
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表面科学
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能源化学
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环境科学
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高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
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2025
·
IF 9.7
Juan Chen,Linmeng Wang,Xiubing Huang,Jingjing Wang,Han Meng,Hongyi Gao,Xiao Chen,Ge Wang
Precise regulation of non-precious metal active species, particularly electron-deficient Ni δ+ centers, is vital yet remains challenging for hydrogenation catalysis. Herein, we propose a synergistic strategy combining ligand anchoring and electronic modulation to construct a metal-organic framework (MOF), designated as CeMIL-101-NH₂ (where MIL stands for materials of institut lavoisier). This strategy enables the generation of ultrasmall Ni δ+ sites, thereby facilitating efficient catalytic hydrogenation. Amino-functionalized ligands (BDC-NH 2 ) offer strong Ni N coordination anchoring ultrasmall Ni nanoparticles, while Ce doping at Cr 2 Ce nodes forms Ce-O-Ni bridges that promote interfacial electron transfer, thereby stabilizing Ni δ+ centers. The Ni@CeMIL-101-NH 2 catalyst exhibits outstanding hydrogenation activity, giving a 100 % selectivity toward tetrahydrodicyclopentadiene (THDCPD) with 100 % conversion of dicyclopentadiene (DCPD) at 100 °C, 2 MPa within 1.5 h, compared with Ni@MIL-101-BDC (19.5 % THDCPD selectivity) and Ni@MIL-101-NH 2 (74.6 % THDCPD selectivity). Replacing Ce with La, Eu, or Fe significantly reduces THDCPD selectivity to 70.6, 25.6, and 4.2 %, respectively. Density functional theoretical (DFT) calculation revealed that the more negative charge density difference (−1.90 vs. -1.85 eV) and more apparent hydrogen spillover processes (0.63 vs. 0.94 eV) in the Ni 4 /CeCr 2 -SBU-NH 2 clusters compared to Ni 10 /Cr-SBU-BDC clusters. Finally, the catalyst maintains high activity and structural integrity over 10 cycles without detectable Ni leaching. The proposed dual optimization strategy offers deep insights for designing efficient and durable MOF-based hydrogenation catalysts.
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PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2025
·
IF 9.7
Shuang Li,Shu-Zhao Sun,Zhi-Wen Wang,Ying-Zhang Shi,Yu-Jie Song,Ling Wu
Constructing dual single-atom catalysts with distinct electronic structures holds significance for the design of catalytic active centers, yet it remains highly challenging. Here, a novel light-induced approach was created to construct Ni 0 and Ni δ+ dual single-atom sites on ZnIn₂S₄ nanosheets (Ni 0 -Ni δ+ /ZIS) for the photocatalytic reduction of CO₂. Characterizations and density functional theory (DFT) calculations results indicate that Ni δ+ and Ni 0 single-atom sites can be selectively anchored in the Zn vacancies and lattice interstitials on the surface of ZIS, respectively. Ni 0 atoms are in a low-spin state without unpaired electrons. In contrast, Ni δ+ atoms are in an intermediate-spin state with an unpaired electron, which can be migrated from the 3d orbital of N δ+ to the 2π u orbitals of CO₂. Ni δ+ and Ni 0 sites decouple the competitive pathways of CO₂ reduction and H₂ evolution via distinct adsorption of H₂O and CO₂ on Ni 0 or Ni δ+ sites (ΔG > 0.5 eV), respectively. Ni 0 sites facilitate the generation of H₂ from H₂O, whereas Ni δ+ sites preferentially reduce CO₂ to CO. Furthermore, the Ni 0 -Ni δ+ dual single-atom sites significantly enhance the efficiency of charge separation and transfer. Therefore, the catalyst attains a high syngas yield of 58.66 mmol·g −1 ·h −1 under visible light, with adjustable CO/H₂ ratios from 1:1.3 to 1:4.1. This work presents a promising light-induced strategy for constructing dual single-atom catalysts via modulating metal electronic structure.
研究领域:
催化
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材料科学
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物理化学
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环境科学
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纳米技术
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产品关联
DOI
PubMed
高影响因子
INORGANIC CHEMISTRY COMMUNICATIONS
·
2026
·
IF 5.9
Zongsheng Chen,Yanxi Ma,Hui Kang,Ting Liu,Hao Song,Ludan Chen,Yingluo He
The development of highly active catalysts for the catalytic conversion of oxygen-containing aromatics in lignite under mild conditions is of crucial importance for the production of clean liquid fuels. In this study, an in situ nitrogen-doped carbon-coated Ni@C/g-C 3 N 4 catalyst was fabricated. The abundant lone-pair electrons on nitrogen atoms within the g-C 3 N 4 support can coordinate with nickel, facilitating the migration of electrons toward the nickel surface. This electron transfer process favors the formation of Ni δ+ active sites with low electron cloud density, thereby enhancing the hydrogenation catalytic activity of the catalyst. The catalyst exhibited exceptional performance in lignite hydrodeoxygenation (HDO): under conditions of 80 °C, 1.5 MPa H 2 , and a reaction time of 1.5 h, 100% conversion of the lignite model compound benzyl phenyl ether (BOB) was achieved. Furthermore, the catalyst demonstrated remarkable hydrodeoxygenation activity, with high selectivity toward various oxygen-containing model compounds, including methyl nonanoate and 2,6-dimethylphenol. The optimal catalyst was applied to the catalytic conversion of the soluble portion (SP) of Naomaohu coal (NMHC). Results indicated that, compared with the SP, the hydrogenated soluble products from catalytic hydrogenation conversion (SP CHC ) showed a significant increase in the variety and quantity of aromatic and alkane compounds, while the relative contents of phenols, alcohols, esters, and ethers were reduced. These findings fully confirm that the Ni@C/g-C 3 N 4 catalyst can effectively cleave C C and C O bonds during the hydrogenation conversion of the SP, providing theoretical guidance for the conversion of lignite into high-quality clean liquid fuels.
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高影响因子
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