CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Xianquan Li,Jifeng Pang,Yujia Zhao,Lin Li,Wenguang Yu,Feifei Xu,Yang Su,Xiaofeng Yang,Wenhao Luo,Mingyuan Zheng
The catalytic synthesis of 1,3-butadiene (1,3-BD) from bio-based ethanol offers an alternative and sustainable process beyond petroleum. However, the intrinsic active sites and corresponding mechanism of 1,3-BD formation have not been fully elucidated yet. By correlating systematic characterization results with catalytic performance, the open Zr species, i.e., Zr(OH)(OSi) 3 moieties, were identified as the active site over the Zr/MFI-BM catalysts for the catalytic transformation of ethanol-acetaldehyde into 1,3-BD. In conjunction with controlled experiments and theory calculations, ethanol and acetaldehyde are proposed to synergistically co-adsorb on the Zr(OH)(OSi) 3 species in a bi-molecular mode, which assists the acetaldehyde condensation and accelerates the critical Meerwein-Ponndorf-Verley-Oppenauer reduction, and accordingly promotes 1,3-BD formation. These findings will stimulate the search towards new metal-zeolite combinations for efficient production of value-added 1,3-BD via biomass-derived ethanol and beyond.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Meng Liu,Caixia Miao,Yumeng Fo,Wenxuan Wang,Yao Ning,Shengqi Chu,Weiyu Song,Ying Zhang,Jian Liu,Zhijie Wu,Wenhao Luo
Precisely tailoring metal single-atoms within zeolite scattfolds and understanding the origin of the unique behavior of such atomically dispersed catalysts are pivotal and challenge in chemistry and catalysis. Herein, we have successfully fabricated Ni single-atoms within BEA zeolite (Ni 1 @Beta) through a facile in situ two-step hydrothermal strategy, notably without using any chelating agent for stabilizing Ni species. With the aid of advanced characterization techniques, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, etc., and combined with density functional theory calculations, the nature and micro-environment of isolated Ni species, which are incorporated within 6-membered rings and stabilized by four skeletal oxygens of Beta zeolite, have been identified. The as-obtained Ni 1 @Beta exhibits a superior performance in terms of activity (with a turnover frequency value up to 114.1 h –1 ) and stability (for 5 consecutive runs) in the selective hydrogenation of furfural, surpassing those of Ni nanoparticle analogues and previously reported Ni-based heterogeneous catalysts. This study provides an efficient strategy for the fabrication of non-noble metal single-atoms within zeolites, which could be of great help for the design of metal-zeolite combinations in the chemoselective reactions involved in biomass conversion and beyond.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Hao Liu,Ying Zhang,Liyang Liu,Tianxiang Chen,Xingcong Zhang,Peng Hu,Chao Xiong,Jie Zhou,Hao Zhang,Lihui Dong,Tsz Woon Benedict Lo,Bing Nan,Xiaohui He,Hongbing Ji
Dispersing metals from nanoparticles to clusters is often achieved using ligand protection methods, which exhibit unique properties such as suppressing structure-sensitive side reactions. However, this method is limited by the use of different metal precursor salts corresponding to different ligands. An alternative approach, the ion exchange (IE) method, can overcome this limitation to some extent. Nevertheless, there is still an urgent need to address the stabilization of metals (especially precious metals) by using IE method. Here, we reported a Pt cluster catalyst prepared mainly by anchoring Pt atoms via O located near the framework Zn in zincosilicate zeolites and riveted by zeolite surface rings after reduction (reduced Pt/Zn-3-IE). The catalyst can achieve an initial propane conversion of 26% in a pure propane atmosphere at 550 °C and shows little deactivation even after 7.5 d of operation. Moreover, the alteration of catalyst by the introduction of framework Zn was also highlighted and interpreted.
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高影响因子
TRANSACTIONS OF NONFERROUS METALS SOCIETY OF CHINA
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2025
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IF 4.7
Pan CHEN,Jia-yan LIU,Ji-hua ZHAI,Yao-hui YANG,Wei SUN
n-octylphosphonic acid (OPA) was introduced as a novel collector for ilmenite flotation and its effectiveness was compared with the conventional chelating collector, benzohydroxamic acid (BHA). Micro-flotation tests demonstrated that OPA was a highly effective and selective collector for separating ilmenite from titanaugite over acidic conditions (optimal pH around 3), which was also supported by adsorption amount measurements. X-ray photoelectron spectroscopy (XPS) tests indicated that the chemisorption of OPA onto ilmenite surface was much stronger than that of BHA. Solution chemistry diagram analyses indicated that OPA could dissociate well at pH 3.0 and mostly exist in anion form. DFT calculations further confirmed that OPA was much easier to adsorb onto ilmenite surface with shorter bond length and lower adsorption energy in comparison with BHA. Therefore, OPA maintained good collecting ability and selectivity for ilmenite flotation in the strongly acidic pulp, providing valuable insights into new collector design and development.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2024
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IF 15.7
Shuyi Li,Changle Mu,Nianqiu He,Jie Xu,Yanping Zheng,Mingshu Chen
ABSTRACT The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al 2 O 3 catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al 2 O 3 catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles , clusters, and single atoms on the surface. Through various dynamic quasi in-situ characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C–C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Jiangyu Tang,Xiao Wang,Yunfa Wang,Min Shi,Peng Huo,Jianxiang Wu,Qiaoxia Li,Qunjie Xu
The oxygen evolution reaction (OER) serves as a fundamental half–reaction in the electrolysis of water for hydrogen production, which is restricted by the sluggish OER reaction kinetics and unable to be practically applied. The traditional lattice oxygen oxidation mechanism (LOM) offers an advantageous route by circumventing the formation of M-OOH* in the adsorption evolution mechanism (AEM), thus enhancing the reaction kinetics of the OER but resulting in possible structural destabilization due to the decreased M–O bond order. Fortunately, the asymmetry of tetrahedral and octahedral sites in transition metal spinel oxides permits the existence of non-bonding oxygen, which could be activated by rational band structure design for direct O-O coupling, where the M–O bond maintains its initial bond order. Here, non-bonding oxygen was introduced into NiFe 2 O 4 via annealing in an oxygen-deficient atmosphere. Then, in-situ grown sulfate species on octahedral nickel sites significantly improved the reactivity of the non-bonding oxygen electrons, thereby facilitating the transformation of the redox center from metal to oxygen. LOM based on non-bonding oxygen (LOM NB ) was successfully activated within NiFe 2 O 4 , exhibiting a low overpotential of 206 mV to achieve a current density of 10 mA cm –2 and excellent durability of stable operation for over 150 h. Additionally, catalysts featuring varying band structures were synthesized for comparative analysis, and it was found that the reversible redox processes of non-bonding oxygen and the accumulation of non-bonding oxygen species containing 2 p holes are critical prerequisites for triggering and sustaining the LOM NB pathway in transition metal spinel oxides. These findings may provide valuable insights for the future development of spinel-oxide-based LOM catalysts.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Mengyang Xu,Bingqing Chang,Jinze Li,Huiqin Wang,Pengwei Huo
The assembly of different Metal organic framework (MOFs) into hybrid heterostructures has proven to be a promising strategy that can effectively break through the limited regulatory capacity of single metal sites. Here, an S-scheme heterostructure (Fe 3 Ni-MOF) based on homologous ligands (1,4-phthalic acid) of ultra-thin Ni-MOF and Fe-MOF nanoparticles with directional electron transport channels, was developed and used it for photoreduction of CO 2 . Under the S-scheme electric field mechanism, the photogenerated carrier can achieve efficient directional separation through Fe–O–Ni atomic bond, which significantly reduces the energy barrier of the rate-determining step. Results show that the performance of Fe 3 Ni-MOF (63.5 μmol g –1 ) was 20 and 3.2 times higher than that of Ni-MOF and Fe-MOF, respectively, and exhibits excellent CO selectivity (96.4%) and stability. Transmission electron microscopy and atomic force microscopy revealed the two-molecular-layers structure of Ni-MOF and the micro-assembly structure of Fe 3 Ni-MOF, which can shorten the electron transport distance and increase the molecular mass transfer rate. X-ray photoelectron spectroscopy, electron spin resonance and electron density difference calculations reveal that interfacial electric fields and atomic bonds work together to promote directional carrier separation, resulting in the accumulation of holes on Ni-MOF and electrons on Fe-MOF. The Gibbs free energy calculation and in-situ Fourier transformed infrared spectroscopy validate that the micro-assembled S-scheme heterostructures with directional electron transport channels can significantly reduce the activation energy barrier of the reaction. This study not only proves the feasibility of constructing MOFs S-scheme heterostructures using homologous ligands, but also provides a new way to overcome the limitations of monometallic MOFs. This strategy is expected to open up a new avenue to design efficient photocatalysts.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Rushuo Li,Tao Ban,Danfeng Zhao,Fajie Hu,Jing Lin,Xiubing Huang,Zhiping Tao,Ge Wang
Defect engineering improves the catalytic performance of metal-organic frameworks (MOFs) loaded metal nanoparticles (MNPs@MOFs), but there is still a challenge in defining the structure-activity relationships. Herein, the content of linker-missing defects in UiO-66(Ce) was systematically regulated via formic acid as the modulators, and defective UiO-66(Ce) loaded Ni nanoparticles (NPs) were constructed for dicyclopentadiene (DCPD) hydrogenation. The fine regulation of defect engineering and reduction conditions affected the structure properties of UiO-66(Ce) and the electronic metal-support interaction between MOFs and Ni NPs, thereby optimizing the microenvironment and electronic state of Ni NPs. The optimized U(Ce)-40eq with suitable defects, small size and structure stability effectively promoted the production of highly dispersed abundant electron-deficient Ni 0 active sites, enhancing the adsorption and activation of H 2 and C=C bonds, especially accelerating the rate-determining step. Therefore, U(Ce)-40eq loaded 5 wt% Ni NPs achieved DCPD saturated hydrogenation to tetrahydrodicyclopentadiene (70 °C, 2 MPa, 90 min), superior to most high-loading Ni-based catalysts. This work reveals the synergistic mechanism of MOFs defect engineering and electronic structure of Ni NPs, providing effective guidance for the precise preparation of highly efficient and stable MNPs@MOFs heterogeneous catalysts.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Jiaxin Li,Yan Lv,Xueyan Wu,Xinyu Guo,Zhuojun Yang,Jixi Guo,Tianhua Zhou,Dianzeng Jia
To address the high cost and limited electrochemical endurance of Pt-based electrocatalysts, the appropriate introduction of transition metal-based compounds as supports to disperse and anchor Pt species offers a promising approach for improving catalytic efficiency. In this study, sub-1 nm Pt nanoclusters were uniformly confined on NiO supports with a hierarchical nanotube/nanosheet structure (Pt/NiO/NF) through a combination of spatial domain confinement and annealing. The resulting catalyst exhibited excellent electrocatalytic activity and stability for hydrogen evolution (HER) and urea oxidation reactions (UOR) under alkaline conditions. Structural characterization and density functional theory calculations demonstrated that sub-1 nm Pt nanoclusters were immobilized on the NiO supports by Pt–O–Ni bonds at the interface. The strong metal-support interaction induced massive charge redistribution around the heterointerface, leading to the formation of multiple active sites. The Pt/NiO/NF catalyst only required an overpotential of 12 and 136 mV to actuate current densities of 10 and 100 mA cm −2 for the HER, respectively, and maintained a voltage retention of 96% for 260 h of continuous operation at a current density of 500 mA cm −2 . Notably, in energy-efficient hydrogen production systems coupled with the HER and UOR, the catalyst required cell voltages of 1.37 and 1.53 V to drive current densities of 10 and 50 mA cm −2 , respectively—approximately 300 mV lower than conventional water electrolysis systems. This study presents a novel pathway for designing highly efficient and robust sub-nanometer metal cluster catalysts.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Yujie Zhan,Chengqin Zhong,Mingli Bi,Yafei Liang,Yuji Qi,Jiaqi Chen,Jiaxu Liu,Xindang Zhang,Shuai Zhang,Yehong Wang,Feng Wang
Iron-Vanadium (FeV) catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde; however, due to its complex compositions, the identification of catalytic active sites still remains challenging, inhibiting the rational design of excellent FeV-based catalysts. Here, in this work, a series of FeV catalysts with various compositions, including FeVO 4 , isolated VO x , low-polymerized V n O x , and crystalline V 2 O 5 were prepared by controlling the preparation conditions, and were applied to methanol oxidation to formaldehyde reaction. A FeV 1.1 catalyst, which consisted of FeVO 4 and low-polymerized V n O x species showed an excellent catalytic performance with a methanol conversion of 92.3% and a formaldehyde selectivity of 90.6%, which was comparable to that of conventional iron-molybdate catalyst. The results of CH 3 OH-IR, O 2 pulse and control experiments revealed a crucial synergistic effect between FeVO 4 and low-polymerized V n O x . It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates, contributing to the high catalytic activity and formaldehyde selectivity. This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.
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CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Jiaxu Liu,Jiaxin Chen,Xiaoyan Zhang,Daidi Fan,Yunpeng Bai
Enzyme catalysis is a promising way to produce chiral products in a green and sustainable way. However, the high cost of cofactors and their relatively low recycling efficiency hinder the widespread application of enzyme catalysis in industry. In contrast, cofactor regeneration and recycling in cells is highly efficient, mainly due to physical effects caused by the ordered spatial organization of enzymes in vivo . The construction of similar catalytic systems with high cofactor recycling in vitro remains challenging. Here, we present a facile method to generate dual enzyme condensates in vitro based on intrinsically disordered region-mediated liquid-liquid phase separation. Typically, a carbonyl reductase from Serratia marcescens ( Sm CR V4 ) and a glucose dehydrogenase from Bacillus megaterium ( Bm GDH) were co-localized in the condensates. This resulted in an up to 20-fold increase in cofactor recycling efficiency (substrate converted per cofactor per unit time), and a 3.4-fold increase in space-time yield compared to the free enzyme system. The reaction enhancement was shown to be highly correlated with the degree of condensation of the dual enzymes. Fluorescence confocal microscopy showed that the cofactor, nicotinamide adenine dinucleotide phosphate (NADPH), was enriched between neighboring enzymes during the reaction due to the proximity effect, facilitating its regeneration and recycling within the condensate. In a scaled-up synthesis, the consumption of NADPH was reduced 50-fold compared to industrial biocatalytic standards, while the condensate still maintained efficient product synthesis. Concentrating multiple enzymes in a nano- and micro-condensate to increase the reaction rate may provide a general and inexpensive method for improving cofactor-involved enzymatic reactions.
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高影响因子
CHINESE JOURNAL OF CATALYSIS
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2025
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IF 17.7
Chao Feng,Jiaxin Shao,Hanyang Wu,Afaq Hassan,Hengpan Yang,Jiaying Yu,Qi Hu,Chuanxin He
It is well known that transition metal sulfides (TMS) (i.e., NiS 2 ) undergo electrochemical reconstructions to generate highly active Ni 3 S 2 during the process of hydrogen evolution reaction (HER) under overpotentials of < 500 mV. However, at higher overpotentials, Ni 3 S 2 can theoretically be further restructured into Ni and thus form Ni/Ni 3 S 2 heterogeneous interface structures, which may provide opportunities to further enhance HER activity of NiS 2 . Here, we selected NiS 2 as a model electrocatalyst and investigated the influence of the reconstruction results induced from regular to ultrahigh overpotentials on its electrocatalytic hydrogen precipitation performance. The experimental results showed that the most significant enhancement of hydrogen precipitation performance was obtained for the NiS 2 @CC-900 (900 means 900 mV overpotential) sample after the ultra-high overpotential induced reconstruction. Compared with the initial overpotential of 161 mV (10 mA cm –2 ), the overpotential of the reconstructed sample reduced by 67 mV (42%). The characterization results showed that an ultra-high overpotential of 900 mV induced deep reconstruction of NiS 2 , formed highly reactive Ni/Ni 3 S 2 heterogeneous interfaces, which is more conducive to improved HER performance and match well with theoretical calculations results. We demonstrated ultrahigh overpotential was an effective strategy to induce NiS 2 deeply reconstruction and significantly improve its HER performance, and this strategy was also applicable to CoS 2 and FeS 2 . This study provides an extremely simple and universal pathway for the reasonable construction of efficient electrocatalysts by induced TMS deeply reconstruction.
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高影响因子
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