Nature Communications
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2025
·Vol. 16
·期 1
·1-10
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IF 15.7
Feng Xiaohui,Jia Haoran,Li Rongtan,Lin Le,Li Mingrun,Chen Mingshu,Liu Chengxiang,Du Xiangze,Wang Xiaoyue,Ding Yunjie,Mu Rentao,Fu Qiang,Bao Xinhe
ZnCrO x oxides coupled with zeolites (OXZEO) allow direct conversion of syngas into light olefins, while active sites in the composite oxides remain elusive. Herein, we find that ZnO particles physically mixed with ZnCr 2 O 4 spinel particles can be well dispersed onto the spinel surfaces by treatment in syngas and through a reduction-evaporation-anchoring mechanism, forming monodispersed ZnO x species with uniform thickness or dimension on ZnCr 2 O 4 up to a dispersion threshold ZnO loading of 16.0 wt% (ZnCr 2 O 4 @ZnO x ). A linear correlation between CO conversion and surface ZnO loading clearly confirms that the ZnO x overlayer on ZnCr 2 O 4 acts as the active structure for the syngas conversion, which can efficiently activate both H 2 and CO. The obtained ZnCr 2 O 4 @ZnO x catalyst combined with SAPO-34 zeolite achieves excellent catalytic performance with 64% CO conversion and 75% light olefins selectivity among all hydrocarbons. Moreover, the ZnO x overlayer is effectively anchored on the ZnCr 2 O 4 spinel, which inhibits Zn loss during the reaction and demonstrates high stability over 100 hours. Thus, a significant interface confinement effect is present between the spinel surface and the ZnO x overlayer, which helps to stabilize ZnO x active structure and enhance the catalytic performance.
研究领域:
催化化学
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材料科学
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PubMed
高影响因子
ChemSusChem
·
2023
·Vol. 16
·期 22
·e202300944
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IF 8.4
Junyu Gao,Fan Wu,Yunxuan Zhao,Xuanang Bian,Chao Zhou,Junwang Tang,Tierui Zhang
Graphical Advanced ZnO/ZnCr 2 O 4 photocatalysts derived from ZnCr-layered double hydroxide (ZnCr-LDH) precursors are successfully synthetized by a simple thermal process. The optimized ZnO/ZnCr 2 O 4 exhibit a considerable ammonia photosynthesis rate of 31.7 μmol g −1 h −1 in pure water, with the origin of the high activity being derived from the high-efficiency carrier separation due to the abundant interfaces. Drawing inspiration from the enzyme nitrogenase in nature, researchers are increasingly delving into semiconductor photocatalytic nitrogen fixation due to its similar surface catalytic processes. Herein, we reported a facile and efficient approach to achieving the regulation of ZnO/ZnCr 2 O 4 photocatalysts with ZnCr-layered double hydroxide (ZnCr-LDH) as precursors. By optimizing the composition ratio of Zn/Cr in ZnCr-LDH to tune interfaces, we can achieve an enhanced nitrogen photofixation performance (an ammonia evolution rate of 31.7 μmol g −1 h −1 using pure water as a proton source) under ambient conditions. Further, photo-electrochemical measurements and transient surface photovoltage spectroscopy revealed that the enhanced photocatalytic activity can be ascribed to the effective carrier separation efficiency, originating from the abundant composite interfaces. This work further demonstrated a promising and viable strategy for the synthesis of nanocomposite photocatalysts for nitrogen photofixation and other challenging photocatalytic reactions.
研究领域:
材料科学
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环境科学
·
化学
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PubMed
高影响因子
Journal of Energy Chemistry
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2026
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IF 15.6
Haoran Jia,Le Lin,Xiaohui Feng,Xiaoyue Wang,Rentao Mu,Qiang Fu
Competitive adsorption between H 2 and CO x ( x = 1, 2) on oxide catalysts represents a primary limitation in hydrogenation reactions, where mutual site blocking suppresses activity and selectivity. This constraint hampers syngas conversion and CO 2 hydrogenation, yet strategies to decouple adsorbates remain elusive. Here, we show that competitive adsorption can be overcome through a partial-site-occupation mechanism that prevents surface saturation and enables independent activation. For a model ZnCr 2 O 4 @ZnO x system, in situ infrared spectroscopy directly reveals the simultaneous adsorption of H 2 with CO or CO 2 , in contrast to the mutually exclusive adsorption observed on pristine ZnO. Kinetic measurements link this decoupling to suppressed inhibition effects and altered reaction orders, driving improved catalytic performance. Density functional theory combined with temperature-programmed analyses further demonstrates that homolytic H 2 dissociation becomes thermodynamically self-limiting, resulting in intrinsically unsaturated surface coverages. These findings indicate competitive adsorption from an inherent constraint to a tunable surface property and establish practical design strategies for cooperative activation in ZnO-based oxide-catalyzed hydrogenation reactions. The ZnCr 2 O 4 -confined ZnO x catalyst decouples the competitive adsorption between CO/CO 2 and H 2 , enabling the co-adsorption and co-activation of these small molecules. Download: Download high-res image (182KB) Download: Download full-size image
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Materials Today Chemistry
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2021
·
IF 8.301
H.J. Gao,S.F. Wang,L.M. Fang,G.A. Sun,X.P. Chen,S.N. Tang,H. Yang,G.Z. Sun,D.F. Li
Nanostructured spinel-type M(M = Mg, Co, Zn)Cr 2 O 4 oxides with novel adsorbents for aqueous Congo red removal were synthesized by a polyacrylamide gel method and studied for their phase structure, microstructure, adsorption performance, and multiferroic behavior. The phase structure and purity analysis revealed that the nanostructured spinel-type M(M = Mg, Co, Zn)Cr 2 O 4 oxides presented a spinel-type cubic structure, and the formation of a secondary phase such as Cr 2 O 3 , MgO , ZnO, or Co 3 O 4 was not observed. The microstructure characterization confirmed that the spinel-type MCr 2 O 4 oxides grew from fine spherical particles to large rhomboid particles. Adsorption experiments of spinel-type MCr 2 O 4 oxides for adsorption of Congo red dye were fitted well with the pseudo-second-order kinetics. The adsorption capacity of the ZnCr 2 O 4 oxide (44.038 mg/g, pH 7, temperature 28 °C, initial dye concentration 30 mg/L) was found to be higher than that of MgCr 2 O 4 oxide (43.592 mg/g, pH 7, temperature 28 °C) and CoCr 2 O 4 oxide (28.718 mg/g, pH 7, temperature 28 °C). The effects of initial adsorbent concentration, initial dye concentration, pH, and temperature between the ZnCr 2 O 4 oxide and Congo red dye at which optimal removal occurs, were performed. The thermodynamic studies confirmed that a high temperature favors the adsorption of Congo red dye onto ZnCr 2 O 4 oxide studied. The nanostructured spinel-type M(M = Mg, Co, Zn)Cr 2 O 4 oxides that exhibited high adsorption performance for adsorption of Congo red dye can be ascribed to the synergistic effect of electrostatic interaction , pore filling, and ion exchange. The present work suggested that the nanostructured spinel-type M(M = Mg, Co, Zn)Cr 2 O 4 oxides have excellent adsorption performance and multiferroic behavior, which shows potential applications for removal of the Congo red dye from wastewater, magnetic memory recording media, magnetic sensor, energy collection and conversion device, and read/write memory.
研究领域:
材料科学
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环境科学
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化学工程
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高影响因子
APPLIED SURFACE SCIENCE
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2026
·
IF 6.6
Liyan Wang,Xiaojun Yang,Yuhang Tan,Yu Li,Zhipeng Wang,Jian Song
Due to the complicated component of ZnCr oxides, the function of the active phases remains controversy, limiting its improvement of catalytic performance for converting syngas to higher alcohols. Herein, a series of ZnCr catalysts with tunable ZnO/ZnCr 2 O 4 molar ratios were fabricated via ball milling of the two individual oxides. Within the ZnO:ZnCr 2 O 4 range of 1:1 to 0.5:1, both CO conversion (18.5%) and isobutanol selectivity (29.0%) were significantly enhanced, while the water‑gas shift reaction and hydrocarbon formation were effectively suppressed. This improved performance originated from synergistic interface effects as revealed by the systematic characterization (XPS, CO‑TPD, and in situ DRIFTS etc.). Lattice distortion and electronic interaction at the interface induced the producing of octahedrally coordinated Zn 2+ sites on ZnCr 2 O 4 , strengthening CO adsorption, meanwhile, ZnO promoted interface hydrogen migration and hydroxyl cycling, steering the CHO* intermediate formation and facilitating C–C coupling. Furthermore, the electron‑rich lattice oxygen at the interface, with moderate basicity, served as active sites for β addition reaction of C 2 intermediate and carbon‑chain growth. These findings clarify the critical role of dual‑phase interface structure in regulating the reaction pathway during syngas conversion, providing a new strategy for the design of high‑performance catalysts for isobutanol synthesis.
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高影响因子
METALLURGICAL AND MATERIALS TRANSACTIONS B-PROCESS METALLURGY AND MATERIALS PROCESSING SCIENCE
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2024
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IF 2.4
Luo Shuxuan,Ma Xingyue,Chen Ziwei,Zhang Lei,Wang Wanlin,Sun Yongqi
Chromium, broadly present in metallurgical systems such as stainless steel slags and vanadium-bearing slags, tends to be in a trivalent form bound in spinel phases due to their ultrahigh stability. To explore the stability of chromium bearing spinels with different divalent cations, herein ACr 2 O 4 (A=Mg, Zn, Mn) spinels were synthesized and stability-tested under both alkaline and acidic environments. X-ray diffraction (XRD) and refinement results reveal that MnCr 2 O 4 exhibited the largest lattice parameters. X-ray photoelectron spectroscopy (XPS) results show that MnCr 2 O 4 had the highest oxygen vacancy concentration, potentially triggering structural instability, consistent with the Fourier-transform infrared (FTIR) and Raman analyses. To further investigate the stability of ACr 2 O 4 spinels in alkaline and acidic environments, we introduced CaO and SiO 2 , respectively, for high temperature calcinations. XRD analyses reveal that ACr 2 O 4 spinels exhibited a high instability under an alkaline condition, with an increasing degree of instability for MgCr 2 O 4 , ZnCr 2 O 4 , and MnCr 2 O 4 successively. We further quantified the relationship between the oxygen vacancy concentrations and the divalent cations containing in spinels as well as the spinel stabilities under an alkaline environment. Under an acidic condition, all ACr 2 O 4 spinels demonstrated a relatively strong structural stability. The understanding of formation and stability of chromium bearing spinels under different conditions could contribute to potential modifications and applications of spinels especially with regard to resource recycling in metallurgy.
研究领域:
材料科学
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环境科学
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冶金学
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高影响因子
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