Nature Communications
·
2024
·Vol. 15
·期 1
·1-12
·
IF 14.7
Liu Yang,Shang Huishan,Zhang Bing,Yan Dongpeng,Xiang Xu
The C–C bond cleavage of biomass-derived glycerol to generate value-added C1 products remains challenging owing to its slow kinetics. We propose a surface fluorination strategy to construct dynamic dual hydrogen bonds on a semiconducting BiVO 4 photoelectrode to overcome the kinetic limit of the oxidation of glycerol to produce formic acid (FA) in acidic media. Intensive spectroscopic characterizations confirm that double hydrogen bonds are formed by the interaction of the F–Bi–F sites of modified BiVO 4 with water molecules, and the unique structure promotes the generation of hydroxyl radicals under light irradiation, which accelerates the kinetics of C–C bond cleavage. Theoretical investigations and infrared adsorption spectroscopy reveal that the double hydrogen bond enhances the C=O adsorption of the key intermediate product 1,3-dihydroxyacetone on the Bi–O sites to initiate the FA pathway. We fabricated a self-powered tandem device with an FA selectivity of 79% at the anode and a solar-to-H 2 conversion efficiency of 5.8% at the cathode, and these results are superior to most reported results in acidic electrolytes.
研究领域:
材料科学
·
光电化学
·
催化反应
✓ 已验证
产品关联
DOI
PubMed
高影响因子
FUEL
·
2022
·
IF 8.035
Baicheng Feng,Zichen Zhang,Jiaqiang Wang,Donglin Yang,Qun Li,Yaping Liu,Hengjun Gai,Tingting Huang,Hongbing Song
The catalytic hydrogenation of carbon dioxide (CO 2 ) into formic acid is among the most important reactions to alleviate global warming and realize the carbon cycle. How to achieve rapid activation of CO 2 remains a challenge. In this work, we designed two novel hydrophobic poly(ionic liquid)s (PILs) with a good affinity for CO 2 . Since the abundant N atoms in the PILs can anchor palladium (Pd) nanoparticles, the designed catalyst can rapidly activate CO 2 and H 2 simultaneously, thus efficiently catalyzing the hydrogenation of CO 2 to formic acid under mild conditions. Due to the synergy from the bis(trifluoromethanesulfonyl)amide anion ([Tf 2 N − ]) with strong hydrophobicity and CO 2 affinity and trimethylamine (NEt 3 ) as a low dissociation energy alkaline additive, the resultant Pd/PIL-bip-Tf 2 N exhibited the best catalytic performance on the hydrogenation of CO 2 to formic acid. The TOF value reached 1,190 h −1 in the aqueous solution of NEt 3 at 100 °C, 1 h, and a total pressure of 4 MPa. The activation energy and dissociation energy during the catalytic process were calculated by DFT, indicating that the synergistic effect of NEt 3 is better than that of other alkaline additives. In addition, the catalytic activity of the catalyst remained stable after several cycling experiments. Based on the obtained results, we proposed a possible reaction pathway. Therefore, PILs have great potential as catalyst carrier material for CO 2 hydrogenation.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Frontiers in Bioengineering and Biotechnology
·
2019
·
IF 5.122
Li Yan,Wen Liyin,Tan Tianwei,Lv Yongqin
The main challenges in multienzymatic cascade reactions for CO2 reduction are the low CO2 solubility in water, the adjustment of substrate channeling, and the regeneration of co-factor. In this study, metal-organic frameworks (MOFs) were prepared as adsorbents for the storage of CO2 and at the same time as solid supports for the sequential co-immobilization of multienzymes via a layer-by-layer self-assembly approach. Amine-functionalized MIL-101(Cr) was synthesized for the adsorption of CO2. Using amine-MIL-101(Cr) as the core, two HKUST-1 layers were then fabricated for the immobilization of three enzymes chosen for the reduction of CO2 to formate. Carbonic anhydrase was encapsulated in the inner HKUST-1 layer and hydrated the released CO2 to HCO3-. Bicarbonate ions then migrated directly to the outer HKUST-1 shell containing formate dehydrogenase and were converted to formate. Glutamate dehydrogenase on the outer MOF layer achieved the regeneration of co-factor. Compared with free enzymes in solution using the bubbled CO2 as substrate, the immobilized enzymes using stored CO2 as substrate exhibited 13.1-times higher of formate production due to the enhanced substrate concentration. The sequential immobilization of enzymes also facilitated the channeling of substrate and eventually enabled higher catalytic efficiency with a co-factor-based formate yield of 179.8%. The immobilized enzymes showed good operational stability and reusability with a cofactor cumulative formate yield of 1077.7% after 10 cycles of reusing.
研究领域:
生物化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Yinuo Wang,Hongming Xu,Ernest P. Delmo,Juhee Jang,Yan Zhang,Tiehuai Li,Xiaoyi Qiu,Zhehan Ying,Ping Gao,Minhua Shao
Electrochemical reduction of CO2 to formic acid for industrial production necessitates not only high selectivity and conversion rate but also efficient CO2 utilization and minimal carbon loss to reduce overall production costs and energy consumption. Despite acidic CO2 reduction reaction being able to greatly alleviate carbon loss, it is often hindered by the aggressive hydrogen evolution reaction and the degradation of catalysts. This study puts forward an effective fluorination-hydrolysis protection mechanism for Sn-based electrocatalysts under acidic conditions. F-doped Sn oxides form a protective layer containing Sn oxide and fluoride, which safeguards the inner reduced Sn from significant degradation in acidic environments. Leveraging this strategy, we achieve impressive performance for formic acid generation without the adverse effects of a violent hydrogen evolution reaction during acidic electrolysis, attaining a Faradaic efficiency of 92% and a partial current density of 722 mA cm–2. This approach not only provides an additional avenue for preventing corrosion of Sn-based catalysts in acidic media but also significantly improves their performance in formic acid production.
研究领域:
电化学
·
材料科学
·
能源转化
✓ 已验证
产品关联
DOI
高影响因子
Nano Energy
·
2019
·
IF 15.548
Yecan Pi,Jun Guo,Qi Shao,Xiaoqing Huang
Perovskite oxides are a class of attractive materials for their broad applications in many energy conversion and storage fields, while their catalytic performance of CO 2 electroreduction (CO 2 ER) has been rarely investigated. Herein, all-inorganic SrSnO 3 perovskite nanowires are constructed and utilized to catalyze the CO 2 ER for the first time. Inspiringly, such SrSnO 3 NWs demonstrates impressive selectivity and activity for formate production, with considerable Faradaic efficiencies (~80%) over a broad potential range, and the highest formate partial current density of 21.6 mA cm −2 , much better than that of the SnO 2 nanoparticles . Further analyses reveal that the notable CO 2 ER activity of SrSnO 3 NWs is linked to the efficient stabilization of formate intermediate (CO 2 •− ) as well as the slow kinetics for hydrogen evolution reaction (HER). This work can inspire the development of highly efficient perovskite catalysts for CO 2 ER and beyond.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2025
·
IF 4.9
Xuetong Liu,Chi Zhang,Nuoyan Li,Runfeng Li,Songlin Lei,Wei Hong,Shuguang Deng,Jun Wang
Herein, a novel and flexible self-supporting gas diffusion electrode (GDE) was fabricated, which including an electrodeposited Bi nanocomposite as a catalyst layer and MIL-101 derived porous carbon in the gas diffusion layer (GDL). Compared with the conventional fabrication of GDE electrodes, the electrodeposition approach can avoid the tedious drop-casting processes of the catalyst layer (CL). The in situ growth mode by electrodeposition can also ensure the firmly interaction between CL and current collector, thus enhancing the stability of the electrode. Meanwhile, the porous carbon derived from MIL-101 which with a high specific area is conducive for the CO 2 enrichment on the electrode, thus facilitate the reaction with high current density. Owe to the special structure, the resultant catalyst showed excellent performance for electrocatalytic CO 2 reduction reaction (CO 2 RR) with enhanced formic acid generation. Notably, at -1.37 V ( vs. RHE), a large current density of 400 mA cm -2 and a high formate Faraday efficiency (FE formate ) of 96.5 % were achieved, and the yield of formic acid reached 46.5 mmol cm -2 h -1 , which is superior to most electrocatalytic catalysts for CO 2 RR. In addition, the FE formate value remained high (>90 %) over a wide voltage window of 800 mV, and the catalyst also maintained stable operation at industrial current density for 70 h. This work provides a new strategy for the design of GDEs with novel structure to achieve high activity and durability for different electrocatalysis.
研究领域:
电化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
Nature Sustainability
·
2025
·
IF 27.1
Li Yunlong,Yin Lichang,Liu Jianan,Qin Xiaolan,Lu Xingyu,Dai Xueya,Qi Ke,Yang Yongqiang,Qi Wei,Liu Gang
Integration of efficient value-added electrochemical oxidation with hydrogen evolution reaction presents a promising sustainable route for both hydrogen energy and the electrochemical refinery industry. However, the serious competition of oxygen evolution reaction (OER) with targeted oxidation reactions at high current densities forms a substantial hurdle for industrial application. Here we report a straightforward approach to inhibit OER side reaction by introducing a trace amount of Cu 2+ into the electrolyte for efficient glycerol oxidation reaction (GOR). Such a strategy enables improved Faradaic efficiency of glycerol to the target product formic acid from 62.2% (without Cu 2+ addition) to 99.3% at a high current density of 800 mA cm −2 . The underlying mechanism is that a reversible redox process of Cu 2+ /Cu + fully suppresses the formation of OER-active-phase hydroxy peroxide on the surface of GOR-active Co 3 O 4 catalyst. The current strategy also applies to other important electrochemical oxidation reactions, paving the way for developing efficient non-OER electrochemical oxidation reactions for various chemical conversion processes.
研究领域:
电化学
·
能源化学
·
催化化学
·
氢能源
·
绿色化工
·
电催化
·
可持续化学
✓ 已验证
产品关联
DOI
高影响因子
Joule
·
2024
·
IF 38.6
Qixing Zhang,Jing Gao,Xinjiang Wang,Jianrong Zeng,Jun Li,Zhongke Wang,Han He,Jingshan Luo,Ying Zhao,Lijun Zhang,Michael Grätzel,Xiaodan Zhang
Tremendous efforts have been made in developing highly selective catalysts for electrochemical CO 2 conversion to formate. However, the rapid deactivation resulting from structural reconstruction and phase transition poses considerable challenges to the system’s durability, particularly at industrially relevant current densities. In this study, we develop a stable hexagonal phase (γ-In 2 S 3 ) catalyst, demonstrating exceptional selectivity toward formate production with a Faradaic efficiency exceeding 90% across a broad current range from −100 to −1,300 mA cm −2 . Theoretical calculations suggest that the formation of sulfur (S) vacancy in γ-In 2 S 3 is impeded under CO 2 reduction conditions, thereby contributing to enhanced electrode stability during electrolysis. Further mechanism studies reveal that the persistence of the S atom enables electron-enriched indium (In)-active sites, likely modifying the adsorption/desorption of the key intermediates for formate production. When coupled with a commercial GaInP/GaAs/Ge triple-junction solar cell, the solar-assisted CO 2 electrolysis reaches a benchmark solar-to-formate conversion efficiency of 14.3% under standard illumination.
研究领域:
电催化
·
可再生能源
·
材料科学
·
二氧化碳利用
·
太阳能燃料
✓ 已验证
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2024
·
IF 18.5
Shuo Wang,Yong Yan,Yongping Du,Yuguo Zhao,Tongxian Li,Dong Wang,Peter Schaaf,Xiayan Wang
Recently, Ni-based chalcogenides havedemonstrated remarkable activity and selectivity for alcohol electrooxidation, but the mechanisms remain debated. This study synthesizes Ni-based electrodeswith different chalcogen anion coordination on nickel nanorod arrays (NiO x /Ni,NiS x /Ni, and NiSe x /Ni NRAs). NiSe x /Ni NRAsshowcases superior performance (Faradaic efficiency 92.9%) in glycerolelectrooxidation reaction (GOR). In situ spectroscopy reveals that NiSecoordination inhibits deep oxidative reconstruction of the Ni-based interface, preventingNiOOH phase formation during GOR, enhancing activity and stability of NiSe x /NiNRAs. Conversely, NiS and NiO coordination lead to deep reconstruction with NiOOHphase formation, limiting GOR performance. Differently, during competingreaction of GOR, the oxygen evolution reaction (OER) leads to deepreconstruction of NiSex interface due to the instability of Ni-Sebonds, inducing performance degradation and dissolution of Se components. Furthermechanism investigation elucidates that the rate-determining step (RDS) ofGOR at the NiSe x interface involves oxidation of *C 2 H 3 O 3 intermediatesthrough H 2 O adsorption, favoring stable formate production.Contrarily, the RDS at the NiS x , NiO x , and NiOOHinterfaces predominantly focus on the decarboxylation of multi-carbon intermediates, raisingenergy barriers and over-oxidizing formate to CO 2 . These results providenew insights for designing Ni-based non-oxide catalysts forefficient and stable electrocatalytic oxidation.
研究领域:
电化学
·
材料科学
·
催化
·
能源材料
✓ 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）