Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60564-0

Hong MA , Siqing CHEN , Jiamin CHEN , Runlong DING , Shaoli LIU , Xinxin TIAN , Jianbing WU , Haitao LI , Yongzhao WANG , Yongxiang ZHAO

Heterogeneous solid frustrated-Lewis-pair (FLP) catalyst is of great promise in practical hydrogenation applications. It has been found that all-solid FLPs can be created on ceria via surface oxygen vacancy regulation. Consequently, it is desired to investigate the mechanisms of the FLP-catalyzed hydrogenation of C=C and C=O and provide insight into the modification of CeO₂ catalysts for the selective hydrogenation. In this work, the reaction mechanism of the hydrogenation of CH₂=CH₂ and CH₃CH=O at the FLP sites constructed on CeO₂(110) surface was investigated by density functional theory (DFT), with the classical Lewis acid-base pairs (CLP) site as the reference. The results illustrate that at the CLP site, the dissociated hydride (H^δ−) forms a stable H−O bond with the surface O atom, while at the FLP site, H^δ− is stabilized by Ce, displaying higher activity on the one hand. On the other hand, the electron cloud density of the Ce atom at the FLP site is higher, which can transfer more electrons to the adsorbed C_C=C and O_C=O atoms, leading to a higher degree of activation for C=C and C=O bonds, as indicated by the Bader charge analysis. Therefore, compared to the CLP site, the FLP site exhibits higher hydrogenation activity for CH₂=CH₂ and CH₃CH=O. Furthermore, at the FLP sites, it demonstrates high efficiency in catalyzing the hydrogenation of CH₂=CH₂ with the rate-determining barrier of 1.04 eV, but it shows limited activity for the hydrogenation of CH₃CH=O with the rate-determining barrier of 1.94 eV. It means that the selective hydrogenation of C=C can be effectively achieved at the FLP sites concerning selective hydrogenation catalysis. The insights shown in this work help to clarify the reaction mechanism of the hydrogenation of C=C and C=O at FLP site on CeO₂(110) and reveal the relationship between the catalytic performance and the nature of the active site, which is of great benefit to development of rational design of heterogeneous FLP catalysts.

非均相固体挫折路易斯对（FLP）催化剂在实际加氢应用中具有广阔的应用前景。研究发现，通过表面氧空位调控，可以在二氧化铈上形成全固体FLPs。因此，希望研究flp催化C=C和C=O加氢的机理，并为CeO2催化剂的选择性加氢改性提供见解。本文以经典的Lewis酸碱对（CLP）位点为参考，利用密度泛函理论（DFT）研究了CeO2（110）表面FLP位点上CH2=CH2和CH3CH=O的加氢反应机理。结果表明，在CLP位点，解离氢化物（Hδ−）与表面O原子形成稳定的H−O键，而在FLP位点，Hδ−被Ce稳定，表现出较高的活性。另一方面，Ce原子在FLP位点的电子云密度更高，可以将更多的电子转移到吸附的CC=C和OC=O原子上，导致C=C和C=O键的激活程度更高，这是Bader电荷分析的结果。因此，与CLP位点相比，FLP位点对CH2=CH2和CH3CH=O表现出更高的加氢活性。此外，在FLP位点上，它对CH2=CH2的加氢具有较高的催化效率，其决定势垒为1.04 eV，但对CH3CH=O的加氢具有有限的催化活性，其决定势垒为1.94 eV。这意味着C=C在选择性加氢催化的FLP位点上可以有效地实现选择性加氢。本工作的发现有助于阐明C=C和C=O在CeO2（110）上FLP位点加氢的反应机理，揭示催化性能与活性位点性质之间的关系，对多相FLP催化剂的合理设计具有重要意义。

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引用次数: 0

Structure-activity relationships and catalytic performances of Ag- and Zn-doped Cu/MOR for methane C−H bond activation Ag和zn掺杂Cu/MOR对甲烷C−H键活化的构效关系及催化性能

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60592-5

Le YANG , Xueyong LÜ , Zile LIU , Zhifeng YAN , Zhijun ZUO

Efficient activation of the C-H bond in methane (CH₄) is critical for achieving methane conversion at low-temperature. In this study, based on theoretical screening using the spin density (ρ) of active O atom as the activity descriptor, density functional theory (DFT) was utilized to investigate the adsorption of CH₄ and the mechanism of the subsequent C−H bond activation on Ag- and Zn-doped [Cu₃O₃]²⁺/mordenite (MOR) surfaces, as well as Zn-doped [CuOCu]²⁺/MOR surfaces, with high ρ values indicating high catalytic activation. The results demonstrated that CH₄ was physisorbed onto active O atom, followed by further activated to yield CH₃' radicals and surface OH groups via the radical reaction mechanism. Both Ag and Zn doping reduced the activation energy and reaction energy for the cleavage of the C−H bond in CH₄, promoting the C−H activation. Further electronic structure analysis revealed the spin polarization of electronic orbitals for both the active O atom and its bonded metal atoms. After Ag doping in [Cu₃O₃]²⁺/MOR, the formation of an Ag–O bond increased the gap between the spin-up and spin-down p-band centers of O 2p (Δε_p) and its spin density, which consequently enhanced the catalytic performance of the active O atom for C−H bond activation in CH₄. Zn doping into both [Cu₃O₃]²⁺/MOR and [CuOCu]²⁺/MOR also increased Δε_p. Specifically, when the Zn 4s and Zn 4p orbitals shifted downward to appropriate low energy levels, Zn 4s and Zn 4p interacted with O 2p to induce half-metallic characteristic in active O atom. This half-metallic characteristic exceptionally promoted C−H bond activation in CH₄, which was insufficiently predicted by the activity descriptors Δε_p and ρ.

甲烷（CH4）中C-H键的有效活化是实现甲烷低温转化的关键。在本研究中，以活性O原子的自旋密度（ρ）作为活性描述符进行理论筛选，利用密度泛函理论（DFT）研究了CH4在Ag-和zn掺杂[Cu3O3]2+/ MOR表面以及zn掺杂[CuOCu]2+/MOR表面的吸附和随后的C−H键活化机理，ρ值越高表明催化活性越高。结果表明，CH4被物理吸附到活性O原子上，然后通过自由基反应机理被进一步活化生成CH3'自由基和表面OH基团。Ag和Zn的掺杂均降低了CH4中C−H键裂解的活化能和反应能，促进了C−H的活化。进一步的电子结构分析揭示了活性O原子及其键合金属原子的电子轨道的自旋极化。Ag在[Cu3O3]2+/MOR中掺杂后，Ag - O键的形成增加了o2p （Δεp）的自旋上下p带中心之间的间隙和自旋密度，从而增强了活性O原子对CH4中C−H键活化的催化性能。Zn掺杂到[Cu3O3]2+/MOR和[CuOCu]2+/MOR中也增加了Δεp。具体来说，当Zn 4s和Zn 4p轨道向下移动到适当的低能级时，Zn 4s和Zn 4p与o2p相互作用，在活性O原子中诱发半金属特征。这种半金属特征特别促进了CH4中C−H键的活化，这是活性描述符Δεp和ρ不能充分预测的。

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引用次数: 0

Study on the enhancement of stability in ambient pressure CO2-FTS for the production of α-olefins by Pt-modified FeZn catalysts pt改性FeZn催化剂提高常压CO2-FTS制备α-烯烃稳定性的研究

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60554-8

Zhangshi LI, Yufeng LI, Huanhuan HE, Changxu WANG, Bing LIU, Xiaohao LIU

The CO₂-FTS under ambient pressure for α-olefins synthesis offers advantages such as safety, lower operating cost, and saving equipment investment. However, the reaction has encountered challenges including high selectivity for CO and CH₄, as well as poor catalyst stability. To address these issues, Cu, Co, Ru, and Pt-modified FeZn catalysts were designed and synthesized for the ambient pressure CO₂-FTS reaction. The results show that the introduction of Pt significantly improves the stability of CO₂ conversion, reducing the selectivity for by-products CO and CH₄, and promoting the formation of valuable C₂₊ hydrocarbon products. When optimized content of 6% Pt was incorporated into the FeZn catalyst, the CO₂ conversion rate increased from 22.5% to 27.3%, and no obvious deactivation was observed over 20 h. Correspondingly, the average selectivity for CO and CH₄ decreased obviously from 93.1% and 52.9% to 80.0% and 20.5%, respectively. Especially, when the H₂/CO₂ ratio was increased from 3 to 7, CO₂ conversion enhanced up to 48.6%, CO selectivity sharply decreased to 24.0%, and at the same time, the selectivity for C₂₊ hydrocarbon products increased noticeably. More importantly, the undesired selectivity to CH₄ was further lower toward about 13.1%, high α-olefins content was achieved like 90%

C_{2}^{=} - C_{4}^{=}

in the C₂−C₄ hydrocarbon fraction, and the selectivity to CO and CH₄ became stable. Characterization results from XRD, H₂-TPR, CO-TPD, CO₂-TPD, H₂-D₂ exchange, TEM, Raman, XPS and MES indicate that the introduction of Pt significantly enhances the adsorption and dissociation of CO, as well as the dissociation of H₂, thus promoting the hydrogenation and coupling of surface CO* species to form C₂₊ hydrocarbons and reducing the carbon deposits. It should be mentioned that the addition of Pt into FeZn catalyst has eliminated the formation of graphite carbon and reduced the thickness of amorphous carbon layer around the iron carbide nanoparticles. Moreover, Pt improves the carbonization ability of Fe species in the catalyst, increases the content of the active phase χ-Fe₅C₂ for FTS, and decreases the crystaline size of χ-Fe₅C₂ particles.

常压CO2-FTS合成α-烯烃具有安全、运行成本低、节省设备投资等优点。但该反应存在CO和CH4选择性高、催化剂稳定性差等问题。为了解决这些问题，设计并合成了Cu、Co、Ru和pt改性FeZn催化剂，用于常压CO2-FTS反应。结果表明，Pt的引入显著提高了CO2转化的稳定性，降低了副产物CO和CH4的选择性，促进了有价C2+烃产物的生成。在FeZn催化剂中掺入6% Pt时，CO2转化率从22.5%提高到27.3%，且在20 h内未出现明显失活现象，CO和CH4的平均选择性分别从93.1%和52.9%明显下降到80.0%和20.5%。特别是当H2/CO2比由3增加到7时，CO2转化率提高到48.6%，CO选择性急剧下降到24.0%，同时对C2+烃产物的选择性显著提高。更重要的是，对CH4的选择性进一步降低，约为13.1%，在C2 -C4烃馏分中，α-烯烃含量达到90%以上，对CO和CH4的选择性趋于稳定。XRD、H2- tpr、CO- tpd、CO2-TPD、H2- d2交换、TEM、Raman、XPS和MES表征结果表明，Pt的引入显著增强了CO的吸附和解离，以及H2的解离，从而促进了表面CO*的加氢和偶联形成C2+碳氢化合物，减少了碳沉积。值得一提的是，在FeZn催化剂中加入Pt消除了石墨碳的形成，降低了碳化铁纳米颗粒周围非晶碳层的厚度。此外，Pt提高了催化剂中Fe种的碳化能力，增加了FTS的活性相χ-Fe5C2的含量，减小了χ-Fe5C2颗粒的结晶尺寸。

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引用次数: 0

Synthesis of FeOx-supported nano-silver catalyst and the mechanism of electrocatalytic epoxidation of propylene feox负载纳米银催化剂的合成及丙烯电催化环氧化机理

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60546-9

Dengwen PI , Xiaobo YANG , Xuning LI

The electrochemical oxidation of propylene offers a promising green process route for propylene oxide (PO) synthesis. However, due to complex by-products and low yields, its development has been hampered. Therefore, it is crucial to explore the reaction mechanism of propylene epoxidation to guide the targeted design of efficient catalysts. In this work, FeO_x-supported nano-silver catalysts (Ag-Fe₂O₃) were designed to achieve the efficient utilization of noble metal Ag to use for the electro-catalytic epoxidation of propylene, and the Ag loading in Fe₂O₃ was regulated by a hydrothermal method combined with a co-precipitation method. When the loading of Ag in Fe₂O₃ is 1.82%, it effectively enhanced the efficiency of the propylene epoxidation reaction, with the Faraday efficiency of 26.2% for PO, and its performance was superior to that of Fe₂O₃ and other samples with different loadings. The bifunctional mechanism was clarified by in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS), where propylene was adsorbed on the surface of Fe₂O₃ and the nano-Ag sites promoted the generation of reactive oxygen species such as *O and *OOH. This work elucidates synergistic catalytic effect between metal and support, provides new mechanistic insights for the electrochemical epoxidation of propylene, and offers possible theoretical guidance for the design of high-performance catalysts.

丙烯的电化学氧化为合成环氧丙烷（PO）提供了一条很有前途的绿色工艺路线。但由于其副产品复杂、产率低，制约了其发展。因此，探索丙烯环氧化反应机理，指导有针对性地设计高效催化剂至关重要。本文设计了feox负载的纳米银催化剂（Ag-Fe2O3），实现了贵金属Ag在丙烯电催化环氧化反应中的高效利用，并采用水热法结合共沉淀法调节了Fe2O3中Ag的负载。Fe2O3中Ag的掺量为1.82%时，能有效提高丙烯环氧化反应的效率，PO的法拉第效率为26.2%，性能优于Fe2O3和其他不同掺量样品。通过原位衰减全反射表面增强红外吸收光谱（ATR-SEIRAS）研究了双功能机理，其中丙烯吸附在Fe2O3表面，纳米ag位点促进了*O和*OOH等活性氧的生成。本研究阐明了金属与载体之间的协同催化作用，为丙烯的电化学环氧化反应提供了新的机理认识，并为高性能催化剂的设计提供了可能的理论指导。

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引用次数: 0

Progress in the modulation strategies of heterogeneous catalysts for ammonia synthesis by nitric oxide reduction 一氧化氮还原合成氨的多相催化剂调控策略研究进展

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60570-6

Na LI , Yanyan YANG , Song YANG , Zhongliang YU

Nitric oxide (NO) is one of the most hazardous pollutants in the atmosphere, posing a serious threat to human health and ecological environment. Traditional treatment methods show high energy consumption and poor economics. New technologies for the efficient conversion of NO to ammonia (NH₃), which are in line with green sustainability, have received widespread attention. However, existing catalysts suffer from numerous problems like their insufficient reactivity, low selectivity, and poor stability. Numerous studies have found that modulation of the catalyst structure can improve these problems. Therefore, this paper reviews the research progress in the modulation strategies of catalysts for the synthesis of NH₃ by reduction NO, and discusses the possible measures that can enhance the catalytic activity, such as energy band modification and electronic modulation, vacancy engineering, elemental doping, and amorphous engineering modulation, etc., as well as the critical factors that influence the catalytic selectivity to NH₃, such as the hydrogen bonding effect and single-atom/highly dispersed sites, etc. In addition, the metal-to-metal/support interactions and the confinement engineering, nano-engineering, and other strategies for strengthening the catalyst stability are also analyzed. Finally, this paper summarizes the challenges faced by this technology in practice and looks into the prospect of this technology in future application.

一氧化氮（NO）是大气中危害最大的污染物之一，对人类健康和生态环境构成严重威胁。传统的处理方法能耗高，经济性差。符合绿色可持续性的NO高效转化为氨（NH3）的新技术受到了广泛关注。然而，现有的催化剂存在反应性不足、选择性低、稳定性差等问题。大量研究发现，调整催化剂结构可以改善这些问题。因此，本文综述了还原NO合成NH3催化剂调制策略的研究进展，讨论了提高催化活性的可能措施，如能带改性和电子调制、空位工程、元素掺杂、非晶态工程调制等，以及影响NH3催化选择性的关键因素。如氢键效应和单原子/高度分散的位点等。此外，还分析了金属与金属/载体之间的相互作用以及约束工程、纳米工程等增强催化剂稳定性的策略。最后，本文总结了该技术在实践中面临的挑战，并展望了该技术在未来应用中的前景。

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引用次数: 0

Application of transition metal doped M-W18O49 in catalysis 过渡金属掺杂M-W18O49在催化中的应用

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60550-0

Duojia REN , Wenxia SHI , Huixiang WANG , Jianghong WU , Wenting LÜ , Ping WANG , Baoliang LÜ

W₁₈O₄₉, a non-stoichiometric n-type semiconductor material with rich oxygen vacancies, exhibits excellent catalytic performance in optical, electrical, and thermal reactions. However, the inherent band structure of pristine W₁₈O₄₉ somewhat limits the enhancement of its catalytic activity. Transition metal ion doping emerges as an effective strategy to modify the internal atomic and electronic structures of this material. By incorporating transition metal atoms into the W₁₈O₄₉ lattice, it not only further increases the concentration of oxygen vacancies and introduces new active sites within W₁₈O₄₉, but also optimizes electron transport and band charge distribution, thereby enhancing its catalytic activity and broadening application scope in catalysis. This paper commences with an overview of the crystalline characteristics and band structure of W₁₈O₄₉, followed by an introduction to the synthesis method of this material. It then elaborates on the current modifications of W₁₈O₄₉ performance through transition metal doping and systematically discusses the typical applications of doped M-W₁₈O₄₉ in catalysis, including the reaction mechanisms involved in photocatalytic CO₂ reduction, photocatalytic and electrocatalytic N₂ fixation, electrocatalytic water splitting, and thermal catalytic oxidative desulfurization.

W18O49是一种富氧空位的非化学计量n型半导体材料，在光学、电学和热学反应中表现出优异的催化性能。然而，原始W18O49固有的能带结构在一定程度上限制了其催化活性的增强。过渡金属离子掺杂是改变这种材料内部原子和电子结构的有效策略。通过在W18O49晶格中加入过渡金属原子，不仅进一步增加了氧空位的浓度，在W18O49中引入了新的活性位点，而且优化了电子传递和带荷分布，从而提高了其催化活性，拓宽了在催化中的应用范围。本文首先概述了W18O49的晶体特性和能带结构，然后介绍了该材料的合成方法。然后阐述了目前通过过渡金属掺杂对W18O49性能的修饰，系统讨论了掺杂M-W18O49在催化中的典型应用，包括光催化CO2还原、光催化和电催化N2固定、电催化水裂解、热催化氧化脱硫等反应机理。

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引用次数: 0

Study on the synthesis of CeO2-Co3O4 catalyst by flame spray pyrolysis method and its catalytic oxidation performance for ethane 火焰喷雾热解法合成CeO2-Co3O4催化剂及其对乙烷的催化氧化性能研究

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60548-2

Xianyan LÜ , Jiangliang HU , Jiancai HOU , Jiancheng WANG , Weiren BAO , Liping CHANG

The Ce₅Co₉₅ catalyst was synthesized using the method of flame spray pyrolysis (FSP) utilizing 2-ethylhexanoic acid (2-EHA) as an organic ligand. The effects on the catalytic oxidation performance of ethane caused by adding 2-EHA to the precursor solvent were systematically studied. The Ce₅Co₉₅-10%2-EHA catalyst exhibits excellent catalytic performance, with a t₉₀ (temperature at which ethane conversion reaches 90%) of 293 °C at a weight hourly space velocity of 60000 mL/(g·h). The catalyst's physicochemical properties were characterized using XRD, BET, Raman, HRTEM, XPS, H₂-TPR, O₂-TPD and EPR techniques, which were effectively correlated with its catalytic performance. The introduction of 2-EHA significantly led to reduction in the catalyst's crystallite size, an increase in the specific surface area, and provision of additional active sites for the reaction. Additionally, it enhanced the Ce-Co interaction, resulting in the creation of abundant oxygen vacancies at the CeO₂-Co₃O₄ interface. This phenomenon not only weakened the metal-oxygen bonds but also promoted the mobility of lattice oxygen, enhancing the catalyst's redox capability and optimizing its oxidation performance. The Ce₅Co₉₅-10%2-EHA catalyst also demonstrated outstanding thermal stability and reversible water tolerance. Moreover, the mechanism of ethane oxidation on the catalyst surface was investigated using in situ diffuse reflectance infrared Fourier transform spectroscopy (in situ DRIFTS).

以2-乙基己酸（2-EHA）为有机配体，采用火焰喷雾热解法（FSP）合成Ce5Co95催化剂。系统地研究了在前驱溶剂中加入2-EHA对乙烷催化氧化性能的影响。Ce5Co95-10%2-EHA催化剂表现出优异的催化性能，在失重时空间速度为60000 mL/（g·h）时，t90（乙烷转化率达到90%的温度）为293℃。采用XRD、BET、Raman、HRTEM、XPS、H2-TPR、O2-TPD和EPR等技术对催化剂的理化性质进行了表征，并与催化剂的催化性能进行了有效关联。2-EHA的引入显著降低了催化剂的晶粒尺寸，增加了比表面积，并为反应提供了额外的活性位点。此外，它增强了Ce-Co相互作用，导致在CeO2-Co3O4界面上产生丰富的氧空位。这种现象不仅削弱了金属-氧键，而且促进了晶格氧的迁移性，增强了催化剂的氧化还原能力，优化了催化剂的氧化性能。Ce5Co95-10%2-EHA催化剂也表现出出色的热稳定性和可逆性耐水性。此外，利用原位漫反射红外傅立叶变换光谱（in situ DRIFTS）研究了乙烷在催化剂表面氧化的机理。

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引用次数: 0

Coal gasification fine slag and nitrogen-containing waste Co-hydrothermal preparation of porous materials for CO2 adsorption 煤气化细渣与含氮废渣共水热法制备吸附CO2的多孔材料

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60560-3

Qingyun WANG , Xiaqing LIU , Li MA , Peng LÜ , Yonghui BAI

A new adsorbent was successfully prepared by hydrothermal treatment and chemical activation through coal gasification fine slag (CGFS) and blue algae (BA) as raw materials and used for CO₂ capture. The CO₂ chemisorption capacity of the adsorbent was further enhanced by taking advantage of the nitrogenous bases contained in the BA. In the hydrothermal process, the addition of BA significantly increased the content of pyrrole nitrogen in the adsorbent. In the activation process, pyrrole nitrogen gradually changed into pyridine nitrogen and graphite nitrogen. Increased BA addition result in a higher specific surface area and microporosity of the adsorbent. The CO₂ adsorption performance test proved that the CGFS-50%-CA sample has the strongest CO₂ adsorption capacity at low temperature, up to 15.59 cm³/g, which is mainly through physical adsorption, and the CGFS-10%-CA sample has the strongest CO₂ adsorption capacity at high temperature, up to 7.31 cm³/g, which is mainly through chemical adsorption. CO₂ uptake of the CGFS-10%-CA sample was well maintained after 10 cycles, with regeneration efficiencies above 99%. The results indicate that the novel adsorbents with coexistence of physical and chemical adsorption have great potential for CO₂ adsorption applications.

以煤气化细渣（CGFS）和蓝藻（BA）为原料，采用水热法和化学活化法制备了一种新型吸附剂，并将其用于CO2捕集。利用BA中所含的氮基，进一步提高了吸附剂对CO2的化学吸附能力。在水热过程中，BA的加入显著提高了吸附剂中吡咯氮的含量。在活化过程中，吡咯氮逐渐转化为吡啶氮和石墨氮。BA添加量的增加导致吸附剂的比表面积和微孔率的增加。CO2吸附性能测试证明，CGFS-50%-CA样品在低温下CO2吸附能力最强，可达15.59 cm3/g，主要通过物理吸附；CGFS-10%-CA样品在高温下CO2吸附能力最强，可达7.31 cm3/g，主要通过化学吸附。经过10次循环后，CGFS-10%-CA样品的CO2吸收率保持良好，再生效率在99%以上。结果表明，这种物理吸附和化学吸附共存的新型吸附剂具有很大的CO2吸附应用潜力。

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引用次数: 0

Nickel-molybdenum alloy electrodeposited on nickel substrates for optimized hydrogen evolution reaction in acidic electrolytes 镍基电沉积镍钼合金，优化酸性电解液中析氢反应

Q3 Energy

燃料化学学报

Pub Date : 2025-10-01 DOI: 10.1016/S1872-5813(25)60547-0

Haibo WANG , Zelin WU , Hui WEN , Zhiyong ZHAO , Chenbo WANG , Tongyu LU , Yuxuan GUO , Congwei WANG , Junying WANG

The utilization of nickel-based catalysts as alternatives to expensive platinum-based (Pt-based) materials for the hydrogen evolution reaction in acidic electrolytes has attracted considerable attention due to their potential for enabling cost-effective industrial applications. However, the unsatisfied cyclic stability and electrochemical activity limit their further application. In this work, nickel-molybdenum (Ni-Mo) alloy catalysts were successfully synthesized through a comprehensive process including electrodeposition, thermal annealing, and electrochemical activation. Owing to the synergistic interaction of molybdenum trinickelide (Ni₃Mo) and molybdenum dioxide (MoO₂) in Ni-Mo alloy, the catalyst display superior overall electrochemical properties. A low overpotential of 86 mV at 10 mA/cm² and a Tafel slope of 74.0 mV/dec in 0.5 mol/L H₂SO₄ solution can be achieved. Notably, remarkable stability with negligible performance degradation even after 100 h could be maintained. This work presents a novel and effective strategy for the design and fabrication of high-performance, non-precious metal electrocatalysts for acidic water electrolysis.

利用镍基催化剂作为昂贵的铂基（pt基）材料在酸性电解质中进行析氢反应的替代品，由于其具有实现经济高效的工业应用的潜力，引起了相当大的关注。但循环稳定性和电化学活性的不理想限制了其进一步的应用。本文通过电沉积、热退火、电化学活化等综合工艺，成功合成了镍钼（Ni-Mo）合金催化剂。在Ni-Mo合金中，由于三氧化二钼（Ni3Mo）和二氧化钼（MoO2）的协同作用，该催化剂表现出优异的综合电化学性能。在0.5 mol/L H2SO4溶液中，可获得低过电位86 mV/ cm2和Tafel斜率74.0 mV/dec。值得注意的是，即使在100小时后，也可以保持显著的稳定性，性能下降可以忽略不计。本研究为设计和制造高性能、非贵金属的酸性电解电催化剂提供了一种新颖有效的策略。

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引用次数: 0

Research on the performance of photothermal catalytic CO2 hydrogenation to methanol using lanthanum- modified copper calcium titanate 镧改性钛酸铜钙光热催化CO2加氢制甲醇的性能研究

Q3 Energy

燃料化学学报

Pub Date : 2025-09-01 DOI: 10.1016/S1872-5813(25)60563-9

LI jianyu , NA wei , GAO wengui , HE pengcheng

Perovskite oxide catalysts of copper calcium titanate with lanthanum (La) substituting for calcium sites were prepared by the sol-gel method, and their performance in the photothermal CO₂ hydrogenation to methanol was experimentally investigated. Techniques such as XRD, SEM, CO₂-TPD, H₂-TPR, XPS, UV-Vis DRS, and EIS were employed to evaluate the advantages of La substitution for the copper calcium titanate catalysts. The results showed that after an appropriate amount of La substitution, the catalyst achieved a methanol space-time yield of 5.788 mmol/(g·h) under 0.8 MPa and 250 ℃ with illumination, which represents a significant improvement in catalytic performance compared to the unsubstituted catalyst. This enhancement is attributed to the promotion of oxygen vacancy formation by La substitution, which enhances the photothermal response efficiency of the catalyst and, consequently, its catalytic activity.

采用溶胶-凝胶法制备了镧取代钙位的钛酸铜钙钙钙氧化物催化剂，并对其在CO2光热加氢制甲醇中的性能进行了实验研究。采用XRD、SEM、CO2-TPD、H2-TPR、XPS、UV-Vis DRS、EIS等技术评价了钛酸铜钙催化剂取代La的优势。结果表明，在0.8 MPa、250℃光照条件下，适量的La取代后，催化剂的甲醇空时产率为5.788 mmol/(g·h)，与未取代的催化剂相比，催化性能有显著提高。这种增强是由于La取代促进了氧空位的形成，从而提高了催化剂的光热响应效率，从而提高了催化活性。

引用次数: 0

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