APPLIED CATALYSIS B-ENVIRONMENTAL
·
2020
·
IF 16.683
Dongyan Shen,Yong Liu,Guangxing Yang,Hao Yu,Peng-Fei Liu,Feng Peng
The electrooxidation of carbon monoxide is a typical example of structure sensitivity in electrocatalysis for fuel cells. Understanding the structure sensitivity is crucial in designing highly efficient catalysts and elucidating reaction mechanisms. Conventionally, only the reactivity of active sites was considered and optimized. However, how the reactant chemically moves to the active site has not been well studied. In this work, we found that CO ad hopping is a general phenomenon on noble metal surfaces such as platinum, iridium, rhodium, and palladium in the case of CO monolayer electrooxidation. Differences in the performances of CO ad stripping on platinum nanoparticles with different surface structures reveal that the CO ad hopping rate is structure sensitive as well. Assisted by a diffusion modeling and density functional theory calculations, it is demonstrated that the structure sensitivity is as a result of a compromise between CO ad chemical diffusivity and reactivity with OH ad .
研究领域:
材料科学
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电化学
·
理论计算
✓ 已验证
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Guozhu Gao,Yong Zhang,Feifei Chen,Meiqin Xu,Chang Sun,Yangfan Song,Weihua Wang,Feng Lu,Hong Dong,Hui Liu,Yahui Cheng
Copper-based catalysts have been established as highly effective for facilitating the electrochemical reduction of carbon dioxide (ECO 2 RR), particularly in the synthesis of multi-carbon (C 2+ ) compounds. However, issues of product selectivity and reaction stability persist, posing significant challenges in the context of high-current-density industrial applications. In this study, we introduce a Cu-enriched Cu 3 N composite catalyst, synthesized via a straightforward magnetron sputtering technique. This catalyst is capable of activating CO 2 and efficiently adsorbing CO, thereby enhancing the electrocatalytic performance for the targeted reactions. At a potential of −1.2 V vs. RHE, the Faradaic efficiency (FE) of the C 2+ product reaches the highest value of 80.39 % with the current density of 267.78 mA cm −2 . Remarkably, the precisely engineered catalyst architecture integrated with a metallic copper (Cu) protective layer demonstrates significantly enhanced ECO 2 RR stability, maintaining C 2+ FE above 79 % for over 10 h at 200 mA cm −2 current density. These results provide a feasible approach for designing and implementing efficient and stable ECO 2 RR catalysts to generate C 2+ products for industrial applications.
研究领域:
材料科学
·
电化学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Jiaming Wang,Huixian Zhong,Kang An,Qiang Liu,Wu Jin,Yuan Liu
In this work, Ni–Co alloy nanoparticles (NPs) on La-doped SiO2 showed excellent selectivity toward ethanol for direct ethanol synthesis via CO hydrogenation. Over the catalyst with an optimal ratio of Ni/Co, the total alcohol selectivity reached 33.5%, of which ethanol occupied 47.0 wt %. The results demonstrated that the interaction between Co and Ni improved the ability to activate H2 and CO and adjusted the amount of the dissociatively and associatively adsorbed CO. Besides, the mutual dilution of nickel and cobalt in Ni–Co alloy NPs effectively reduced the isolated Co or Ni-clusters; thus, the formation of heavy hydrocarbons was suppressed. In the reaction process, Ni@Co–Co2C, a core–shell composite with a nickel core and Co–Co2C shell, was formed, which suppressed the loss of nickel species. Moreover, with the reaction going on, a small amount of poorly alloyed Co-clusters would be covered gradually by the formed coke, resulting in an increase in alcohol selectivity.
研究领域:
催化化学
·
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2022
·
IF 9.224
Shuohan Yang,Yonghou Xiao,Wuyue Zhang,Yu Qiao,Qidong Zhao,Ning Zhang,Gaohong He
Cuprous ion-based zeolites have been proven as promising carbon monoxide (CO) adsorbents by virtue of their excellent adsorption and regeneration properties due to π complexation. However, existing preparation methods still suffer from the problems of a cumbersome process and low loading amounts of cuprous ions. Herein, we proposed a one-step synthesis strategy of using ethanol as a solvent to provide a reducing protective environment, which enabled the facile and controllable preparation of highly dispersed CuCl over 5A zeolites. Using CuCl as a copper source, to ensure the integrity of the 5A zeolite structure, CuCl species were directly loaded onto the 5A support in one step. Ethanol solution could effectively protect Cu(I) from being oxidized by oxygen in air and improve the stability of cuprous ions in Cu(I)/5A adsorbents. The results demonstrated that the Cu(I)/5A prepared by this method exhibited a superior CO adsorption performance to the pristine 5A zeolite. The adsorption capacity of CO over Cu(I)/5A attained 3.44 mmol·g–1 at 298 K and atmospheric pressure, which was evidently superior to those of CuY (2.7 mmol·g–1) and CuSAPO34 (1.84 mmol·g–1) reported in the literature, while the adsorption capacity of H2 was only 0.069 mmol·g–1 under the same condition. According to the ideal solution adsorption theoretical model, CO was preferentially adsorbed and the IAST selectivity of CO in the CO/H2 binary mixture over Cu(I)/5A was about 273.4. This study provides a novel and effective way to synthesize high-efficiency CO adsorbents.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2024
·
IF 3.8
Zhenfei Wang,Congli Li,Lei Tang,Jiahui Yang,Qi Shi,Jinxiang Dong
Ni-MOF-74 is among the most promising candidates for CO adsorption due to its highest CO adsorption capacity. However, the feasibility of using Ni-MOF-74 in actual CO/N2 pressure swing adsorption (PSA) processing cannot be reliably inferred based solely on its adsorption capacity at normal temperature and pressure. Hence, we systematically studied its CO working capacity and regenerability at different test temperatures and pressure ranges by single-component static and binary-component dynamic (CO/N2, 50%/50% and 30%/70%, v/v) experiments. The static experiments preliminarily indicated an appropriate operating temperature of 100 °C with adsorption–desorption pressures in the range of 3.0–0.1 bar for the PSA process. The working capacity and regenerability of CO were evaluated as 3.41 mmol·g–1 and 66.21% (adsorption–desorption pressure: 3.0–0.1 bar, 100 °C). A higher temperature reduces the binding force between CO and Ni-MOF-74, so that more CO is desorbed, which leads to an increase in the working capacity and regenerability of CO. Furthermore, through CO/N2 binary-component dynamic breakthrough experiments, the optimal operating temperature and CO adsorption partial pressure for the PSA process were determined as 100 °C and 1.5 bar at a total desorption pressure of 0.2 bar. Typically, for a CO/N2 composition of 50%/50%, the CO working capacity and regenerability were 2.66 mmol·g–1 and 85.25% at 100 °C and a CO partial pressure of 1.5 bar (total CO adsorption pressure of 3.0 bar) at a total desorption pressure of 0.2 bar. These results may guide PSA process design and optimization for adsorbents with strong CO binding ability.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Sustainable Chemistry & Engineering
·
2024
·
IF 7.1
Yonghou Xiao,Qiang Guo,Shuohan Yang,Qidong Zhao,Gaohong He
The cuprous-ion-based zeolites constructed by introducing Cu(I) adsorption active sites into zeolite Linde Type A have proved to be efficient in carbon monoxide (CO) adsorption with high selectivity and capacity. However, how to directly fabricate zeolite 4A containing copper species and effectively overcome cuprous ion aggregation during the preparation process is still a challenge. Here, we propose an efficient fabrication method to synthesize highly dispersed Cu(I)-modified octahedral zeolite 4A adsorbents using a molecular complex formed by a hydrogel with a silicon/aluminum molar ratio of 1:1, copper ions, and tetramethylammonium hydroxide (TMAOH) as the template. Zeolite 4A containing copper ions was directly obtained by incorporating the precursor of cuprous ions into the confined space between zeolite 4A channel walls and TMAOH. The target zeolite Cu(I)/4A adsorbent with highly dispersed Cu(I) was constructed after introducing VCl3 as the reducing agent via the solid-state dispersion method during the process of removing the template. In comparison with pristine zeolite 4A, a bimodal microporous pore size distribution was observed in as-synthesized Cu(I)/4A. Cu(I)/4A exhibited an enhanced static (1.15 mmol/g) and dynamic (0.0016 mmol g−1) CO adsorption capacity, respectively, at 25 °C and 1 bar. Moreover, Cu(I)/4A displayed a lower H2 adsorption capacity under identical conditions. Through calculation using the ideal adsorption solution theoretical (IAST) equation, the CO selectivity from the CO/H2 mixture on Cu(I)/4A attained ca. 16.95. Therefore, Cu(I)/4A with highly dispersed Cu(I) was successfully fabricated, and its excellent CO adsorption selectivity and capacity enable it to be potentially applied for the actual deep separation of CO/H2.
研究领域:
材料科学
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化学工程
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2018
·Vol. 6
·期 19
·8930-8939
·
IF 9.931
Yu-Xia Li,Shuai-Shuai Li,Ding-Ming Xue,Xiao-Qin Liu,Meng-Meng Jin,Lin-Bing Sun
Cu(I)-containing materials have great potential in various applications such as in CO adsorption; however, development of an efficient and controllable method to produce Cu(I) sites remains a significant challenge; herein, a two-step double-solvent (DS) strategy is reported for the first time to fabricate Cu(I) sites in a representative metal–organic framework, MIL-101(Cr); this strategy ensures that both introduction of the Cu(II) precursor and its reduction to Cu(I) occur inside the pores and significantly minimizes the aggregation of Cu species. This is difficult to realize through conventional methods used for Cu(II) introduction (wet impregnation) or reduction (liquid-phase reduction). The two-step DS strategy involves selective reduction of Cu(II) to form Cu(I) without the formation of any Cu(0). The obtained Cu(I)-containing materials exhibit an excellent CO adsorption capacity (up to 2.42 mmol g−1) at 298 K and 1 bar, much better than that of the benchmark adsorbents including CuCl/γ-Al2O3 (1.0 mmol g−1), CuCl/MCM-41 (0.57 mmol g−1), and CuZSM-5 (0.11 mmol g−1).
研究领域:
材料科学
·
化学工程
✓ 已验证
DOI
高影响因子
DALTON TRANSACTIONS
·
2024
·Vol. 53
·期 26
·10919-10927
·
IF 3.5
Xuanzhao Lu,Baozhen Yuan,Yi Liu,Li-Xia Liu,Jun-Jie Zhu
Electrochemical reduction of carbon dioxide (CO2) or carbon monoxide (CO) to valuable multi-carbon (C2+) products like acetate is a promising approach for a sustainable energy economy. However, it is still challenging to achieve high activity and selectivity for acetate production, especially in neutral electrolytes. Herein, a bioinspired hemin/Cu hybrid catalyst was developed to enhance the surface *CO coverage for highly efficient electroreduction of CO to acetate fuels. The hemin/Cu electrocatalyst exhibits a remarkable faradaic efficiency of 45.2% for CO-to-acetate electroreduction and a high acetate partial current density of 152.3 mA cm−2. Furthermore, the developed hybrid catalyst can operate stably at 200 mA cm−2 for 14.6 hours, producing concentrated acetate aqueous solutions (0.235 M, 2.1 wt%). The results of in situ Raman spectroscopy and theoretical calculations proved that the Fe–N4 structure of hemin could enhance the CO adsorption and enrich the local concentration of CO, thereby improving C–C coupling for acetate production. In addition, compared to the unmodified Cu catalysts, the Cu catalysts functionalized with cobalt phthalocyanine with a Co–N4 structure also exhibit improved acetate performance, proving the universality of this bioinspired molecule-enhanced strategy. This work paves a new way to designing bioinspired electrolysis systems for producing specific C2+ products from CO2 or CO electroreduction.
研究领域:
电化学
·
催化材料
·
能源化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2024
·
IF 5.8
Jihai Zhao,Qi Wang,Yaowen Wang,Xinbo Li,Chang Liu,Taotao Huang,Liping Li,Guangshe Li
The spin state of transition metal ions, specifically controlled by the electrons in antibonding orbital, is recognized as a descriptor for heterogeneous catalysts. However, the influence of spin state on the adsorption of CO molecular with two electrons in the highest occupied molecular orbital, has been overlooked. In this work, the Co 2+ spin states in multicomponent rock-salt oxides are regulated by increasing configurational entropy, demonstrating the impact of Co 2+ spin states on CO adsorption. The CO catalytic oxidation activity of as-synthesized rock-salt oxides exhibits a volcano-shaped relationship with the ratio of Co 2+ in high spin state to Co 2+ in low spin state. Mg 0.33 Co 0.33 Ni 0.33 O with this spin state ratio of 7.5 has the largest negative adsorption energy to CO molecular and exhibits the best catalytic activity. The findings on the relationship between the spin state of transition metal ions and reactant adsorption can contribute to the understanding of catalytic activity at the electronic level.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
ENVIRONMENTAL SCIENCE AND POLLUTION RESEARCH
·
2024
·Vol. 31
·期 14
·21267-21278
·
IF 0
Zhao Dongling,Geng Linlin,Jia Yanfei,Wei Jianwen,Zhou Xiaobin,Liao Lei
High-temperature solid adsorbent Li 4 SiO 4 has received broad attention due to its high theoretical adsorption capacity, high regeneration capacity, and wide range of raw materials for preparation. In this paper, a Li 4 SiO 4 adsorbent was prepared by MCM-48 as the silica precursor and modified by doping with metal ions (Ca 2+ and Na + ) for high-temperature capture of low-concentration CO 2 . The results showed that the surface of the Ca-doped (or Na-doped) Li 4 SiO 4 adsorbent developed some particles that are primarily composed by Li 2 CaSiO 4 (or Li 3 NaSiO 4 ). Furthermore, the grains of the adsorbents became finer, effectively increasing the specific surface area and enhancing adsorption performance. Under 15 vol% CO 2 , the maximum CO 2 adsorption was 25.63 wt% and 32.86 wt% when the Ca 2+ doping amount was 0.06 and the Na + doping amount was 0.12, respectively. These values were both higher than the adsorption capacity before the metal ion doping. After 10 adsorption/desorption cycles, the adsorption capacity of Na-doped Li 4 SiO 4 increased by 9.68 wt%, while that of Ca-doped Li 4 SiO 4 decreased by 7.98 wt%. This difference could be attributed to the easy sintering of the Ca-containing adsorbent. Furthermore, a biexponential model was used to fit the CO 2 adsorption curve of the adsorbent in order to study the adsorption kinetics. Compared to the conventional Li 4 SiO 4 , the Ca/Na-doped adsorbent offers several advantages, such as a high CO 2 adsorption capacity and stable cycling ability.
研究领域:
材料科学
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环境工程
·
化学工程
·
吸附技术
✓ 已验证
DOI
ACS Catalysis
·
2021
·
IF 13.084
Kaili Wang,Danyang Huang,Yichi Guan,Feng Liu,Jia He,Yi Ding
Designing highly efficient and durable electrocatalysts for methanol oxidation reaction (MOR) plays a decisive role in the commercialization of direct methanol fuel cells (DMFCs). Compared with commercial Pt/C catalysts, fine-tuning the electronic structure of electrocatalysts to reduce the adsorption energy of CO while at the same time increasing the adsorption energy of OH is beneficial to improving the activity of MOR. Herein, ultrastable self-supported PtCu nanowires (NWs) with abundant Cu-vacancies have been developed, wherein the CO adsorption energy is weakened by doping of Cu elements and the OH adsorption energy is strengthened by the vacancy defect through dealloying. The well-designed PtCu NWs exhibit an outstanding performance for the MOR, with a specific activity 7.5 times higher than that for the commercial Pt/C catalyst, which transcends most electrocatalysts’ performance currently. Moreover, the stability of PtCu electrocatalysts is greatly improved over 1 h owing to a “non-CO” pathway for MOR. Further DMFC tests present a 2 times higher power density than that of commercial Pt/C, and the PtCu integrated DMFC also presents a higher stability for 24 h, transcending most Pt-based anode catalysts of DMFCs.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2019
·
IF 8.456
Junfang Ding,Liping Li,Haorui Zheng,Ying Zuo,Xiyang Wang,Huixia Li,Shaoqing Chen,Dan Zhang,Xingliang Xu,Guangshe Li
Nanomaterials are widely used as redox-type reaction catalysts, while reactant adsorption and O2 activation are hardly to be promoted simultaneously, restricting their applications in many important catalytic fields such as preferential CO oxidation (CO-PROX) in H2-rich stream. In this work, an interface-enhanced Co3O4–CuCoO2 nanomesh was initially synthesized by a hydrothermal process using aluminum powder as a sacrificial agent. This nanomesh is systematically characterized by powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption, X-ray photoelectron spectroscopy, UV–vis absorption spectroscopy, Raman spectroscopy, X-ray absorption near-edge spectroscopy, hydrogen temperature-programmed reduction, and oxygen temperature-programmed desorption. It is demonstrated that the nanomesh possesses high-density nanopores, enabling a large number of CO adsorption sites exposed to the surface. Meanwhile, electron transfer from O2– to Co3+/Co2+ and the weakened bonding strength of Co–O bond at surfaces promoted the oxygen activation and redox ability of Co3O4. When tested as a catalyst for CO-PROX, this nanomesh with an optimized pore structure and a surface electronic structure, exhibits a strikingly high catalytic oxidation activity at low temperatures as well as a broader operation temperature window (i.e., CO conversion >99.0%, 100–200 °C) in the CO selective oxidation reaction. The present finding should be highly useful in promoting the quest for better CO-PROX catalysts, a hot topic for proton exchange membrane fuel cells and automotive vehicles.
研究领域:
催化材料
·
能源化学
·
燃料电池
✓ 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）