JOURNAL OF ENVIRONMENTAL MANAGEMENT
·
2021
·
IF 6.789
Xiao Xia,Liqiang Zhang,Zhanyao Li,Xueliang Yuan,Chunyuan Ma,Zhanlong Song,Guifang Chen
CaSO 4 reduction decomposition for CaO preparation provides a theoretical basis for the utilization of the industrial byproduct, gypsum. In this study, the effects of temperature (950 °C–1150 °C), CO 2 /CO partial-pressure ratio (1–15), CO concentration (1%–5%), and O 2 concentration (1%–7%) on the preparation of CaO from CaSO 4 by CO reduction decomposition under different reaction atmospheres were investigated. The physical properties of CaO prepared by the decomposition of CaSO 4 and CaCO 3 were analyzed and compared. Finally, the reaction mechanism of the reduction decomposition of CaSO 4 to CaO by CO was studied. The findings reveal that CaSO 4 can be completely decomposed into CaO when the reaction temperature exceeds 1000 °C, CO% ≥ 2%, and P(CO 2 )/P(CO) ≥ 8. Furthermore, the addition of an appropriate amount of O 2 can improve the yield of CaO in the products. In an O 2 –CO–N 2 atmosphere, where O 2 % = 7% and CO% = 16%, CaSO 4 can be completely decomposed into CaO without the addition of CO 2 . The physical properties of CaO prepared by the reduction and decomposition of CaSO 4 are better than those prepared by the calcination of CaCO 3 . An analysis of the reaction mechanism of the reduction decomposition of CaSO 4 by CO reveals that CaSO 4 generates CaO and CaS simultaneously. In addition, CaS can react with unreacted CaSO 4 to form CaO. Furthermore, it can react with CO 2 to produce CaO if an appropriate amount of CO 2 is added to the reaction atmosphere. The secondary interactions of CaS with CaSO 4 and CO 2 can significantly improve the yield of CaO in the product.
研究领域:
化学工程
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of the American Chemical Society
·
2024
·
IF 14.4
Qiliang Liu,Qike Jiang,Ling Li,Wenxing Yang
Understanding the reconstruction of electrocatalysts under operational conditions is essential for studying their catalytic mechanisms and industrial applications. Herein, using spatiotemporally resolved Raman spectroscopy with CO as a probe molecule, we resolved the spontaneous reconstruction of Cu active sites during cathodic CO reduction reactions (CORRs). Quasi-in situ focused ion beam transmission electron microscopy (FIB-TEM) revealed that under prolonged electrolysis, the Cu surface can reconstruct to form nanometer-sized Cu particles with (111)/(100) facets and abundant grain boundaries, which strongly favor the formation of an inactive *CObridge binding site and deteriorate the CORR performance. A short period of anodic oxidation can efficiently remove these reconstructed nanoparticles by quick dissolution of Cu, thus providing an effective strategy to regenerate the Cu catalysts and recover their CORR performance. This study provides real-time in situ observations of Cu reconstruction and changes in the binding of key reaction intermediates, highlighting the decisive role of the local active site, rather than the macroscopic morphology, on adsorption of key reaction intermediates and thus CORR performance.
研究领域:
电化学
·
催化科学
✓ 已验证
DOI
PubMed
高影响因子
ADVANCED MATERIALS
·
2020
·Vol. 32
·期 39
·2002382
·
IF 27.398
Changming Zhao,Gan Luo,Xiaokang Liu,Wei Zhang,Zhijun Li,Qian Xu,Qinghua Zhang,Huijuan Wang,Deming Li,Fangyao Zhou,Yunteng Qu,Xiao Han,Zezhou Zhu,Geng Wu,Jing Wang,Junfa Zhu,Tao Yao,Yafei Li,Henny J.M. Bouwmeester,Yuen Wu
Electrochemical reduction of CO to value-added products holds promise for storage of energy from renewable sources. Copper can convert CO into multi-carbon (C 2+ ) products during CO electroreduction. However, developing a Cu electrocatalyst with a high selectivity for CO reduction and desirable production rates for C 2+ products remains challenging. Herein, highly lattice-disordered Cu 3 N with abundant twin structures as a precursor electrocatalyst is examined for CO reduction. Through in situ activation during the CO reduction reaction (CORR) and concomitant release of nitrogen, the obtained metallic Cu° catalyst particles inherit the lattice dislocations present in the parent Cu 3 N lattice. The de-nitrified catalyst delivers an unprecedented C 2+ Faradaic efficiency of over 90% at a current density of 727 mA cm −2 in a flow cell system. Using a membrane electrode assembly (MEA) electrolyzer with a solid-state electrolyte (SSE), a 17.4 vol% ethylene stream and liquid streams with concentration of 1.45 m and 230 × 10 −3 m C 2+ products at the outlet of the cathode and SSE-containment layer are obtained.
研究领域:
材料科学
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电化学
·
能源存储与转化
✓ 已验证
产品关联
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2025
·
IF 21.1
Wei Wei,Zhenyao Li,Jitao Shang,Chenxi Xia,Xuli Hu,Yangshun Hu,Junchen Xu,Yan Zhao,Mingyue Ding
The selective electrochemical reduction of CO to valuable multi-carbon (C 2 + ) products is a key strategy for mitigating global warming and addressing the energy crisis. Nevertheless, the activity and selectivity of CO-to-C 2+ products conversion remain low due to the lack of effective catalysts. In this study, bimetallic CuPd was grown in situ on Cu nanoparticles via a seed-mediated approach, constructing a stable CuPd/Cu interface for the CO reduction reaction (CORR). The CuPd alloy promotes CO adsorption and hydrogenation, resulting in abundant and stable *COH intermediates over catalytic sites. Consequently, a stable asymmetric coupling is established at the CuPd/Cu interface, lowering the reaction energy barrier and facilitating C-C coupling. A high acetate selectivity of 49 % was achieved at –1.0 V versus the reversible hydrogen electrode (RHE) with a current density of 349 mA/cm². This study highlights the critical role of constructing CuPd/Cu asymmetric sites for C–C coupling, paving the way for designing highly selective catalysts that enhance C 2+ product formation and acetate production.
研究领域:
材料科学
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电化学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
Journal of the American Chemical Society
·
2025
·
IF 15.6
Wen Yan,Tiantian Wu,Jia Liu,Zhe Zheng,Ming Ma
Electrolyte cation identity has been reported to influence the multicarbon (C2+) selectivity in CO2/CO electroreduction. However, most of the previous work for cation size effect is based on H-cell configurations, which may inadvertently distort the underlying mechanism of cation effect due to mass transport limitations, particularly for CO reduction. Here, using GDE-type flow electrolyzers, we report that the selectivity of total C2+ products on Cu is independent of alkali cation identity (Li+, Na+, K+, and Cs+) in the absence of the CO transport limitation. Notably, a high concentration of strongly hydrated cation (such as Li+) inhibits the total C2+ formation in CO reduction, whereas total C2+ selectivity is retained upon increasing concentrations of weakly hydrated cation (such as K+). Further investigations reveal that the CO coverage at a low cation concentration is almost independent of the cation identity, but the CO coverage at highly concentrated cations strongly relies on the alkali cation identity.
研究领域:
电化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Ruijie Ma,Huimin Gao,Jinpeng Zhang,Jieying Jing,Wen-Ying Li
Photocatalytic reduction of CO 2 to formic acid (HCOOH) offers a sustainable pathway for carbon utilization, yet its efficiency is fundamentally limited by poor CO 2 adsorption and rapid electron-hole recombination in conventional photocatalysts. To address this challenge, a series of Pd-loaded hydrogenated TiO 2 catalysts (x wt%Pd/H-TiO 2 ) were developed through a synergistic hydrogen reduction-impregnation strategy, aiming to regulate the electron density of Pd active sites and enhance interfacial charge separation. Systematic characterization revealed that increasing Pd loading (0.6–1.4 wt%) effectively trapped photogenerated electrons, suppressing recombination losses and elevating electron density at Pd sites. Combined with optimized CO 2 adsorption capacity (0.178 mmol·g −1 ) and accelerated charge transfer, the 1.0 wt%Pd/H-TiO 2 catalyst achieved a HCOOH production rate of 14.14 mmol·g cat −1 ·h −1 under mild conditions (30 °C, 2.0 MPa, 4.57 mW·cm −2 ), outperforming most reported TiO 2 -based systems. Mechanistic studies further demonstrated a strong correlation between Pd-induced electronic effects and multi-electron CO 2 activation kinetics. This work provides a scalable catalyst design paradigm for balancing charge dynamics and surface reactivity in photocatalytic CO 2 valorization.
研究领域:
环境催化
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材料科学
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能量转换
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纳米技术
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2024
·Vol. 15
·期 1
·1-11
·
IF 14.7
Yang Xiaoju,Rong Chao,Zhang Li,Ye Zhenkun,Wei Zhiming,Huang Chengdi,Zhang Qiao,Yuan Qing,Zhai Yueming,Xuan Fu-Zhen,Xu Bingjun,Zhang Bowei,Yang Xuan
Developing in situ/operando spectroscopic techniques with high sensitivity and reproducibility is of great importance for mechanistic investigations of surface-mediated electrochemical reactions. Herein, we report the fabrication of highly ordered rhombic gold nanocube superlattices (GNSs) as substrates for surface-enhanced infrared absorption spectroscopy (SEIRAS) with significantly enhanced SEIRA effect, which can be controlled by manipulating the randomness of GNSs. Finite difference time domain simulations reveal that the electromagnetic effect accounts for the significantly improved spectroscopic vibrations on the GNSs. In situ SEIRAS results show that the vibrations of CO on the Cu 2 O surfaces have been enhanced by 2.4 ± 0.5 and 18.0 ± 1.3 times using GNSs as substrates compared to those on traditional chemically deposited gold films in acidic and neutral electrolytes, respectively. Combined with isotopic labeling experiments, the reaction mechanisms for C-C coupling of CO electroreduction on Cu-based catalysts are revealed using the GNSs substrates.
研究领域:
电化学
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表面科学
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材料科学
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光谱学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF LUMINESCENCE
·
2024
·
IF 3.3
Jingshan Hou,Jie Shi,Langping Dong,Jianghua Wu,Ganghua Zhang,Haijie Chen,Wei Gao,Yongzheng Fang
The discovery of pure-red emitting phosphor is great meaningful for the achievement of high color rendering index white light emitting diodes , but still a challenge due to the strict crystal field limitations. In this work, we demonstrate the preparation of a 630 nm pure-red emitting Ca 3 Si 2 O 7 :Eu 2+ phosphor for the first time through a CO reduction strategy. The changes in crystal field strength caused by different methods for the preparation of Ca 3 Si 2 O 7 :Eu 2+ are investigated and discussed based on the understanding of the thermodynamic theory and structure resolution. Finally, a white light-emitting diode with a high color rendering index (Ra = 98) is accomplished by combining the as-prepared Ca 3 Si 2 O 7 :Eu 2+ pure-red emitting phosphor with a 375 nm chip and the commercial used blue and green phosphors. The results also demonstrate the generalizability of the weak reduction strategy for the exploration of “redder” Eu 2+ doped phosphors.
研究领域:
材料科学
·
光电子学
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固态物理
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无机化学
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照明技术
✓ 已验证
DOI
高影响因子
Nature Catalysis
·
2025
·
IF 44.6
Liu Qiliang,Yang Wenxing
Non-covalent interactions between the electrocatalyst surface and its electrolyte play a vital role in shaping the microenvironments of electrochemical interfaces. Yet, direct spectroscopic investigation of these interactions and their catalytic effects has remained elusive in electrocatalysis research. Here, using in situ Raman spectroscopy, we resolve a universal change of interfacial water structure at electrified Cu surfaces during alkaline CO reduction reaction. An intricate non-covalent interaction between interfacial water and surface hydroxyl (OH ad ) was recognized through a proposed OH ad ···M + (H 2 O) n complex, with M + representing electrolyte cations. On exposure to catalytic potentials, these non-covalent complexes evolve into local OH − ···M + (H 2 O) n species residing within the electrical double layer and favour CO reduction reaction into acetate over other C 2 products. These results demonstrate the crucial roles of non-covalent interactions in determining the activity of surface reactions, whose existence and rational design may offer opportunities for future fine control of electrocatalysis processes.
研究领域:
电催化
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表面化学
·
物理化学
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光谱学
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能量转换
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-10
·
IF 16.6
Ding Jie,Wei Zhiming,Li Fuhua,Zhang Jincheng,Zhang Qiao,Zhou Jing,Wang Weijue,Liu Yuhang,Zhang Zhen,Su Xiaozhi,Yang Runze,Liu Wei,Su Chenliang,Yang Hong Bin,Huang Yanqiang,Zhai Yueming,Liu Bin
In this work, via engineering the conformation of cobalt active center in cobalt phthalocyanine molecular catalyst, the catalytic efficiency of electrochemical carbon monoxide reduction to methanol can be dramatically tuned. Based on a collection of experimental investigations and density functional theory calculations, it reveals that the electron rearrangement of the Co 3d orbitals of cobalt phthalocyanine from the low-spin state (S = 1/2) to the high-spin state (S = 3/2), induced by molecular conformation change, is responsible for the greatly enhanced CO reduction reaction performance. Operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy measurements disclose accelerated hydrogenation of CORR intermediates, and kinetic isotope effect validates expedited proton-feeding rate over cobalt phthalocyanine with high-spin state. Further natural population analysis and density functional theory calculations demonstrate that the high spin Co 2+ can enhance the electron backdonation via the d xz / d yz −2π* bond and weaken the C-O bonding in *CO, promoting hydrogenation of CORR intermediates.
研究领域:
电化学
·
催化
·
材料科学
·
理论化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry C
·
2024
·Vol. 12
·期 22
·8145-8152
·
IF 5.7
Dongkai Hu,Mavlanjan Rahman,Shuifu Liu,Lina Shen,Pengpeng Dai,Dawei Wen,Mingmei Wu
While numerous approaches have been devised to optimize the luminescence properties of Eu2+-activated phosphors, the quest for a simple design strategy to achieve color-tunable Eu2+ emission remains a significant challenge. Here, we present a straightforward, doping-free method to tailor the site occupation of Eu2+ and modify its luminescence properties. In the pristine sample, the NaBaB9O15 (NBB) host featuring two cation sites (Na+ and Ba2+), Eu2+ exclusively occupies the Ba2+ site, resulting in blue emission when the NBB:Eu2+ phosphor is synthesized in a H2 reducing atmosphere. When we use CO instead of a H2 reducing atmosphere, impressively, the formation energy required for heterovalent substitution of Na+ by Eu2+ is lowered, leading to the emergence of a distinct green emission band. Significantly, the resultant phosphor NBB:Eu2+@CO exhibits not only a high internal quantum yield of 85.1% and zero-thermal-quenching behavior within the temperature range of 25–200 °C but also wavelength-tunable emission. Benefitting from the multi-color luminescence of the NBB:Eu2+@CO phosphor, its optical applications will no longer be confined to general lighting but extend to anti-counterfeiting and encryption. This study provides a novel design methodology for optimizing the optical properties of Eu2+-activated phosphors.
研究领域:
材料科学
·
光学
·
化学
✓ 已验证
DOI
高影响因子
CHINESE JOURNAL OF CATALYSIS
·
2025
·
IF 17.7
Xianlong Lu,Lili Wang,Xueyang Zhao,Binbin Pan,Zhendong Li,Xiangfei Du,Shihan Zhang,Fan Dong,Bangwei Deng
Copper (Cu)-based catalysts show significant potential for producing high value-added C 2+ products in electrocatalytic CO 2 /CO reduction reactions (CO (2) RR). However, the structural reconfiguration during operation poses substantial challenges in identifying the intrinsic catalytic active site, especially under similar mass transport conditions. Herein, three typical and commercial Cu-based catalysts (Cu, CuO, and Cu 2 O) are chosen as representatives to elucidate the structure-activity relationship of CORR in the membrane electrode assembly electrolyzer. Notably, only the Cu catalyst demonstrates the most suppression of hydrogen evolution reaction, thus achieving the highest FE of 86.7% for C 2+ products at a current density of 500 mA cm –2 and maintaining a stable electrolysis over 110 h at a current of 200 mA cm –2 . The influence of chemical valence state of Cu, electrochemical surface area, and local pH were firstly investigated and ruled out for the significant FE differences. Finally, based on the structure analysis from high resolution transmission electron microscope, OH – adsorption, in situ infrared spectroscopy and density functional theory calculations, it is suggested that the asymmetric C-C coupling ( via *CHO and *CO) is the most probable reaction pathway for forming C 2+ products, with Cu (100)-dominant grain boundaries (GBs) being the most favorable active sites. These findings provide deeper insights into the synergistic relationship between crystal facets and GBs in electrocatalytic systems.
研究领域:
电化学
·
催化
·
材料科学
·
纳米技术
·
物理化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）