Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Wang Pu,Zhang Xingyu,Shi Run,Zhao Jiaqi,Waterhouse Geoffrey I. N.,Tang Junwang,Zhang Tierui
The selective oxidative dehydrogenation of ethane (ODHE) is attracting increasing attention as a method for ethylene production. Typically, thermocatalysts operating at high temperatures are needed for C–H activation in ethane. In this study, we describe a low temperature ( < 140 °C) photocatalytic route for ODHE, using O 2 as the oxidant. A photocatalyst containing PdZn intermetallic nanoparticles supported on ZnO is prepared, affording an ethylene production rate of 46.4 mmol g –1 h –1 with 92.6% ethylene selectivity under 365 nm irradiation. When we employ a simulated shale gas feed, the photocatalytic ODHE system achieves nearly 20% ethane conversion while maintaining an ethylene selectivity of about 87%. The robust interface between the PdZn intermetallic nanoparticles and ZnO support plays a crucial role in ethane activation through a photo-assisted Mars-van Krevelen mechanism, followed by a rapid lattice oxygen replenishment to complete the reaction cycle. Our findings demonstrate that photocatalytic ODHE is a promising method for alkane-to-alkene conversions under mild conditions.
研究领域:
化学工程
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材料科学
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能源科学
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产品关联
DOI
PubMed
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Zhenyao Li,Wei Wei,Xuli Hu,Zhen Zhang,Yangshun Hu,Yushan Wu,Yao Wang,Junchen Xu,Mingyue Ding
While engineering lattice strain has been proven effective in enhancing the electrochemical CO 2 reduction performance of a catalyst, the correlation between strain effect and the intrinsic catalytic mechanism has remained elusive. Herein, a photolithography-inspired method is proposed to regulate Cu(111) lattice strain. By irradiating the photosensitive Cu(Acac) sol–gel, Acac chelate bond undergoes π→π * electronic transition, and the ring-closed Cu(Acac) decompose into the stabilized Cu(Acac) mesh which presents as nanospots embedded onto the surface of the Cu cluster. The photoinduced nanospots serve to exert compressive strain to the Cu(111) lattice in which the lattice distance is reduced by 5.7–11.4%. Herein, the catalyst with 11.4% lattice compression exhibits enhanced C 2 H 4 production capabilities, reaching a maximal Faradaic efficiency of 57.00%, and a high partial current density of 456.01 mA cm −2 . Theoretical calculations reveal that the compressed Cu(111) lattice exhibits reduced surface energies, leading to a significant drop in the C─C coupling reaction free energy from 1.16 eV over the pristine lattice, to 0.57 eV over the 10% compressed lattice. Additionally, the 10% compressed lattice facilitates spontaneous *O splitting immediately after OC─CHO coupling which leads to the generation of C 2 H 4 -favoring *CCH intermediate.
研究领域:
材料科学
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电化学
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催化反应
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理论计算
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产品关联
DOI
高影响因子
ACS Catalysis
·
2021
·
IF 13.084
Yanliang Zhou,Yicong Chai,Xiaoyu Li,Zihao Wu,Jian Lin,Yujia Han,Lin Li,Haifeng Qi,Yiming Gu,Leilei Kang,Xiaodong Wang
Selective oxidative dehydrogenation (ODH) of light alkanes to alkenes over metal oxides usually obeys a redox catalysis cycle, where the release and recovery of lattice oxygen play a key role in catalytic performance. Therefore, it remains a challenge to prepare metal oxides with limited reducibility, such as TiO2, as a dominant active component rather than as a support or modifier in this process. Here, we find a significant increase of ethane ODH performance over a layered TiO2 (M-TiO2) catalyst, which is in situ evolved from a Ti3C2Tx MXene material during the reaction. The reactivity of this M-TiO2 is 4 times higher than that of P25 TiO2, with an excellent ethylene productivity of 15.4 gC2H4 gcat–1 h–1 that outperforms the previously reported catalysts. Experimental characterizations and theoretical calculations reveal the importance of Ti and oxygen vacancy defects over M-TiO2 on the conversion of C2H6. The Ti vacancy sites can stabilize the defective structure and increase the reducibility of lattice oxygen to reduce the activation energy barrier of ethane, while the oxygen vacancy sites facilitate the activation of O2 to recover lattice oxygen.
研究领域:
催化化学
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材料科学
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理论计算
✓ 已验证
DOI
高影响因子
Chem
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2022
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IF 25.832
Lu Liu,Huan Li,Hang Zhou,Shengqi Chu,Lujie Liu,Zhaochi Feng,Xuedi Qin,Jizhen Qi,Jue Hou,Qinming Wu,Hangjie Li,Xi Liu,Liwei Chen,Jianping Xiao,Liang Wang,Feng-Shou Xiao
Summary Catalytic dehydrogenation of ethane (EDH) is promising for the utilization of shale gas to produce ethylene, but the current processes mostly exhibit space-time productivity of ethylene lower than 1.5 Kg C2H4 Kg cat −1 h −1 because of the insufficient catalyst activity in the non-oxidative route. We reported a catalyst with isolated cobalt in siliceous zeolite derived from a mechanically assisted spontaneous dispersion. This material can operate as a non-oxidative EDH catalyst at thermodynamically limited conversion levels under rapid gas feeding, resulting in ethylene productivity at 13.4 Kg C2H4 Kg cat −1 h −1 . This result is superior to that of the previous non-noble metal catalysts and even outperforms the precious PtSn/Al 2 O 3 catalyst. The isolated cobalt sites are preserved upon calcination at high temperatures and during EDH operation under harsh conditions, resulting in superior durability in a long reaction period with negligible coke formation.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
ChemCatChem
·
2023
·Vol. 15
·期 4
·e202201413
·
IF 4.5
Dandan Zhao,Shaoyang Zhang,Tianyu Guo,Qiang Zhao,Jianping Du,Jinping Li
Graphical Carbon dioxide reduction : The rectangular nanoflakes with crystalline/amorphous phase structures that the square nanoblocks are confined in amorphous nanoflakes efficiently enhance the electrocatalytic conversion of CO 2 to ethylene. The electrocatalytic reduction of CO 2 to high value-added chemicals is one of the effective technologies to achieve the goal of carbon neutralization. However, highly selective production of hydrocarbon via electrochemical conversion of CO 2 still has great challenges. Herein, a unique CuO phase composition is constructed that consists of rectangular nanoflakes possessing crystalline/amorphous structures by the facile strategy. Crystalline CuO square nanoblocks are confined in amorphous nanoflakes and form crystalline/amorphous hybrid phase. The results of electrocatalytic CO 2 reduction demonstrate that this crystalline/amorphous CuO material exhibits superior CO 2 conversion ability with ethylene Faradaic efficiency of 58.3 % at −1.08 V vs. RHE, which is ascribed to nanoflake structures and fast electron transfer on the crystalline/amorphous interfaces because of superior conductivity of amorphous CuO. The present research provides an effective route to reconstruct novel crystalline/amorphous interfaces of CuO for catalysis applications.
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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产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-10
·
IF 15.7
Wei Fen,Zhao Jiwu,Liu Yu-Chun,Hsu Yung-Hsi,Hung Sung-Fu,Fu Junwen,Liu Kunlong,Lin Wei,Yu Zhiyang,Tan Li,Lu Xue Feng,Feng Chengyang,Zhang Huabin,Wang Sibo
Lattice oxygen-mediated photocatalytic ethane dehydrogenation represents a sustainable strategy for ethylene production, yet achieving a balance between high productivity, selectivity, and durability remains challenging. Here, we report a defective NiO-300 catalyst, where precisely engineered Ni vacancies activate lattice oxygen by weakening Ni–O bond and improving lattice oxygen mobility. This promotes efficient ethane activation and C–H bonds cleavage through photoinduced hole capture, intensifying ethane dehydrogenation via a light-boosted Mars-van Krevelen mechanism. The NiO-300 catalyst manifests a high ethylene yield of 604.5 μmol g −1 h −1 with 100% selectivity and stability over 200 cycles. In situ spectroscopic and theoretical studies elucidate the generation of active oxygen species, the evolution of Ni coordination, the formation of key intermediates, and the underlying photocatalytic mechanism. Our findings highlight cation vacancy engineering as a powerful tactic to fully activate lattice oxygen for solar-driven alkene production from alkane dehydrogenation over oxide photocatalysts.
研究领域:
催化
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材料科学
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化学工程
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物理化学
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纳米技术
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产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2025
·
IF 21.1
Guangming Wang,Junnan Chen,Ye Qu,Yingjun Dong,Keting Wang,Lihua Qian,Rong Fu,Ying Zhang,Hui-Ming Cheng,Xiaolong Zhang
Electrochemical CO 2 reduction (ECR) to produce chemicals and fuel is a promising technique to build a net-zero carbon circular economy. The performance of ECR has largely advanced in the past decade along with the application of gas diffusion electrodes (GDEs). However, the gas-liquid balance in GDEs is highly fragile due to inefficient CO 2 mass transfer in catalyst layers, which is prone to cause the decay of catalytic performance. In this study, integrated Cu electrodes with controllable mesopores are designed and prepared by copolymer mediated electroless deposition. The optimized Cu electrode shows a selectivity of 81 % (including 65 % for C 2 H 4 ) towards C 2+ products, with a maximum C 2+ partial current density of 232 mA∙cm −2 . Further characterization and simulations reveal that the interconnected mesoporous channels stacked by in-situ reduced Cu nanoparticles leads to an improved CO 2 supply near catalytic sites. In addition, a micro-environment boosting the retention, protonation of *CO intermediates and a unique *CO-CHO coupling step is formed. Our findings provide valuable guidance for enhancing mass transfer and C-C coupling in ECR by creating and controlling intrinsic mesoporous structures in catalyst layers.
研究领域:
电化学
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材料科学
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二氧化碳利用
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纳米材料
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可持续能源
✓ 已验证
产品关联
DOI
高影响因子
Nature Energy
·
2022
·Vol. 7
·期 9
·835-843
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IF 67.439
Li Wenzheng,Yin Zhenglei,Gao Zeyu,Wang Gongwei,Li Zhen,Wei Fengyuan,Wei Xing,Peng Hanqing,Hu Xingtao,Xiao Li,Lu Juntao,Zhuang Lin
Many CO 2 electrolysers under development use liquid electrolytes (KOH solutions, for example), yet using solid-state polymer electrolytes can in principle improve efficiency and realize co-electrolysis of CO 2 and pure water, avoiding corrosion and electrolyte consumption issues. However, a key challenge in these systems is how to favour production of multicarbon molecules, such as ethylene, which typically necessitates a strong alkaline environment. Here we use bifunctional ionomers as polymer electrolytes that are not only ionically conductive but can also activate CO 2 at the catalyst–electrolyte interface and favour ethylene synthesis, while running on pure water. Specifically, we use quaternary ammonia poly(ether ether ketone) (QAPEEK), which contains carbonyl groups in the polymer chain, as the bifunctional electrolyte. An electrolyser running on CO 2 and pure water exhibits a total current density of 1,000 mA cm − 2 at cell voltages as low as 3.73 V. At 3.54 V, ethylene is produced with the industrial-scale partial current density of 420 mA cm − 2 without any electrolyte consumption.
研究领域:
电化学
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材料科学
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能源技术
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产品关联
DOI
高影响因子
Nature Communications
·
2021
·Vol. 12
·期 1
·1-11
·
IF 14.919
Sun Hao,Chen Ling,Xiong Likun,Feng Kun,Chen Yufeng,Zhang Xiang,Yuan Xuzhou,Yang Baiyu,Deng Zhao,Liu Yu,Rümmeli Mark H.,Zhong Jun,Jiao Yan,Peng Yang
Electrochemical CO 2 reduction (CO 2 RR) in a product-orientated and energy-efficient manner relies on rational catalyst design guided by mechanistic understandings. In this study, the effect of conducting support on the CO 2 RR behaviors of semi-conductive metal-organic framework (MOF) — Cu 3 (HITP) 2 are carefully investigated. Compared to the stand-alone MOF, adding Ketjen Black greatly promotes C 2 H 4 production with a stabilized Faradaic efficiency between 60-70% in a wide potential range and prolonged period. Multicrystalline Cu nano-crystallites in the reconstructed MOF are induced and stabilized by the conducting support via current shock and charge delocalization, which is analogous to the mechanism of dendrite prevention through conductive scaffolds in metal ion batteries. Density functional theory calculations elucidate that the contained multi-facets and rich grain boundaries promote C–C coupling while suppressing HER. This study underlines the key role of substrate-catalyst interaction, and the regulation of Cu crystalline states via conditioning the charge transport, in steering the CO 2 RR pathway.
研究领域:
电化学
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材料科学
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催化
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能源转换
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产品关联
DOI
PubMed
高影响因子
FUEL
·
2025
·
IF 7.5
Ying Li,Haibo Zhao
Ethylene production via chemical looping oxidative dehydrogenation (CL-ODH) of ethane faces a critical challenge in balancing conversion efficiency and selectivity due to competing oxygen species requirements. Here, we present a bifunctional composite catalyst (CrH/BiCZ) by physically integrating a Cr-HZSM5 (Cr-H) dehydrogenation (DH) catalyst with a Bi 2 O 3 -Ce 0.4 Zr 0.6 O 2 (Bi-CZ) selective hydrogen combustion (SHC) catalyst. This tandem system decouples ethane activation and hydrogen combustion, promoting the DH process of ethane through the in situ hydrogen combustion of the SHC catalyst. The Ce-Zr solid solution in Bi-CZ acts as an oxygen reservoir, enabling complete H 2 combustion within 3 min and suppressing carbon deposition. This rapid hydrogen combustion shifts the reaction equilibrium towards ethylene production. At 650 °C, the optimized CrH/BiCZ catalyst achieves 84.1 % ethylene selectivity at 43.0 % ethane conversion, and maintains exceptional stability over 36 redox cycles. This work establishes a scalable chemical looping strategy for efficient ethylene synthesis.
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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反应工程
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能量转换
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产品关联
DOI
高影响因子
Chemical Science
·
2024
·Vol. 15
·期 24
·9173-9182
·
IF 7.6
Jiye Feng,Wenbiao Zhang,Danni Shi,Yingshuai Jia,Yi Tang,Yuying Meng,Qingsheng Gao
Multi-phase interfaces are promising for surmounting the energy barriers of electrochemical CO2 reduction involving multiple electron transfer steps, but challenges still remain in constructing interfacial micro-structures and unraveling their dynamic changes and working mechanism. Herein, highly active Ag/Cu/Cu2O heterostructures are in situ electrochemically restructured from Ag-incorporating HKUST-1, a Cu-based metal–organic framework (MOF), and accomplish efficient CO2-to-C2H4 conversion with a high faradaic efficiency (57.2% at −1.3 V vs. RHE) and satisfactory stability in flow cells, performing among the best of recently reported MOFs and their derivatives. The combination of in/ex situ characterizations and theoretical calculations reveals that Ag plays a crucial role in stabilizing Cu(I) and increasing the CO surface coverage, while the active Cu/Cu2O interfaces significantly reduce the energy barrier of C–C coupling toward the boosted ethylene production. This work not only proves MOFs as feasible precursors to derive efficient electrocatalysts on site, but also provides in-depth understanding on the working interfaces at an atomic level.
研究领域:
材料科学
·
电化学
·
催化
·
能量转换
✓ 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）