INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES
·
2022
·Vol. 23
·期 13
·7381
·
IF 6.208
Daqian Wang,Zhihao Zhang,Shuchuan Xu,Ying Guo,Shifei Kang,Xijiang Chang
Defective functional-group-endowed polymer semiconductors, which have unique photoelectric properties and rapid carrier separation properties, are an emerging type of high-performance photocatalyst for various energy and environmental applications. However, traditional oxidation etching chemical methods struggle to introduce defects or produce special functional group structures gently and controllably, which limits the implementation and application of the defective functional group modification strategy. Here, with the surface carboxyl modification of graphitic carbon nitride (g-C3N4) photocatalyst as an example, we show for the first time the feasibility and precise modification potential of the non-thermal plasma method. In this method, the microwave plasma technique is employed to generate highly active plasma in a combined H2+CO2gas environment. The plasma treatment allows for scalable production of high-quality defective carboxyl group-endowed g-C3N4nanosheets with mesopores. The rapid H2+CO2plasma immersion treatment can precisely tune the electronic and band structures of g-C3N4nanosheets within 10 min. This conjoint approach also promotes charge-carrier separation and accelerates the photocatalyst-catalyzed H2evolution rate from 1.68 mmol h−1g−1(raw g-C3N4) to 8.53 mmol h−1g−1(H2+CO2-pCN) under Xenon lamp irradiation. The apparent quantum yield (AQY) of the H2+CO2-pCN with the presence of 5 wt.% Pt cocatalyst is 4.14% at 450 nm. Combined with density functional theory calculations, we illustrate that the synergistic N vacancy generation and carboxyl species grafting modifies raw g-C3N4materials by introducing ideal defective carboxyl groups into the framework of heptazine ring g-C3N4, leading to significantly optimized electronic structure and active sites for efficient photocatalytic H2evolution. The 5.08-times enhancement in the photocatalytic H2evolution over the as-developed catalysts reveal the potential and maneuverability of the non-thermal plasma method in positioning carboxyl defects and mesoporous morphology. This work presents new understanding about the defect engineering mechanism in g-C3N4semiconductors, and thus paves the way for rational design of effective polymeric photocatalysts through advanced defective functional group engineering techniques evolving CO2as the industrial carrier gas.Keywords:g-C3N4;carboxyl group;defect engineering;non-thermal plasma method;CO2utilization
研究领域:
材料科学
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光催化
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能源与环境科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of CO2 Utilization
·
2019
·
IF 5.189
Fengjia Xie,Rong Chen,Xun Zhu,Qiang Liao,Dingding Ye,Biao Zhang,Youxu Yu,Jinwang Li
Carbon dioxide (CO 2 ) as greenhouse gas is the primary cause of global warming. One of the ideal routes to remedy CO 2 emission is to transform it to hydrocarbons by photocatalytic reduction of CO 2 . However, poor yield and product selectivity of photocatalytic reduction of CO 2 pose significant challenges to its widespread applications. To address this critical issue, a coupled system that integrates photocatalytic reduction of CO 2 with photocatalytic fuel cell (PFC) is developed for direct power generation using CO 2 . In this coupled system, the products by photocatalytic reduction of CO 2 works as the fuels for the PFC to directly generate electricity. Direct power generation by this coupled system is demonstrated via only in the presence of CO 2 as the input under illumination. A short circuit current density of 0.175 mA/cm 2 and a maximum power output of 0.110 mW/cm 2 are yielded for the case with the supply of CO 2 , which are much higher than those without CO 2 . Moreover, it is interesting to find that the fuel concentrations at the PFC outlet are even higher than those at the PFC inlet, implying that the coupled system proposed in this study can not only generate the electricity but also yield the solar fuels. This work opens a new avenue for the CO 2 utilization toward direct power generation.
研究领域:
环境科学
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能源工程
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化学工程
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 15
·9581-9585
·
IF 12.732
Yuemin Du,Yijie Liu,Sixie Yang,Chao Li,Zhu Cheng,Feilong Qiu,Ping He,Haoshen Zhou
The fossil fuel crisis and global warming are becoming more and more severe in this century, while the exploration of human survival on Mars is being pushed forward steadily. Hence, it is meaningful to effectively utilize CO2, the main greenhouse gas and a major component of the Martian atmosphere. Due to their high capacity and ability to capture CO2, Li–CO2 batteries have received much attention. However, there are problems that still need to be solved relating to Li–CO2 batteries, including the instability of the electrolyte and the non-negligible polarization caused by the formation and decomposition of Li2CO3. To address these issues, an all-solid-state Li–CO2 battery, which uses RuO2 nanoparticles combined with single-walled carbon nanotubes (SWCNTs) as the cathode material and a sodium super ionic conductor (NASICON)-type ceramic solid electrolyte, Li1.5Al0.5Ge1.5(PO4)3 (LAGP), has been developed and it operates over a broad temperature range. Under a pure CO2 atmosphere, this well-designed battery shows a discharge capacity of 2499 mA h g−1 and a charge capacity of 2137 mA h g−1 in the first cycle at 60 °C, and stable cycling performance over 30 cycles under a capacity limitation of 500 mA h g−1 at a current density of 50 mA g−1. This result enhances the possibility of the utilization of the Li–CO2 battery in the future.
研究领域:
材料科学
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能源技术
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催化化学
✓ 已验证
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Ren Bohua,Zhang Xiaowen,Yang Leixin,Wen Guobin,Dong Silong,Xiong Haoyang,Liu Yiyin,Duan Xiaoman,Tan Lichao,Wang Xin,Chen Zhongwei
Electrocatalytic upgrade of CO 2 offers a promising approach for recycling of global CO 2 emissions, facilitating the achievement of carbon neutrality. Nevertheless, direct utilization of practical dilute CO 2 is urgently important yet rather difficult, which is hindered by the balance of reaction kinetics and mass transport of CO 2 to the catalytic sites. Herein, we propose coordinating the local environment and active catalyst by constructing covalent organic frameworks (COF) on single-atomic In-doped Cu 2 O (In 1 @Cu 2 O) for a high tolerance of CO 2 inlet concentrations (15% to 100%). The optimized amounts of COF functionalized by the trifluoromethyl group act as the local CO 2 /CO diffusion channels via steric confinement effects and C···F electronic effects. Besides, the formation of key intermediates for C 2+ products is greatly facilitated by the promoted COOH adsorption. Hence, a total current of 81.7 A is realized in a 4 × 100 cm 2 electrolyzer stack with over 770 mmol/h C 2+ products at an inlet of dilute CO 2 . Such a electrode architecture sheds light on the dilute CO 2 electrolysis at the potential industrial scale.
研究领域:
电化学
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环境催化
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能源材料
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碳中和
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工业电解
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Guangjun Ji,Cunyao Li,Benhan Fan,Guoqing Wang,Zhao Sun,Miao Jiang,Lei Ma,Li Yan,Yunjie Ding
Rational designing the structure of catalysts is an effective but challenging way to optimize catalytic performance for target reaction, which is especially significative in the field of single site catalysts. In this work, a kind of single Rh catalysts for heterogeneous hydroformylation of olefins with CO 2 as substituted carbonyl sources was designed. By simply doping N sites surround Rh P active sites, Rh 1 /POPs-P&N were endowed with better catalytic performance even than homogeneous Rh P complex catalysts. Our study showed that the fine fabricated skeleton structure of Rh 1 /POPs-P&N could endow the N sites with function promotion effect on the adjacent Rh P active sites to different degrees. Consequently, the Rh 1 / m -POP-PPh 3 &PMPD, which formed more HRh(CO) 2 (P) 2 species during the reaction, exhibited the highest yield of aldehydes (conversion of 89 %, selectivity toward aldehydes of 87.1 %, l/b ratio of 13.1), good stability (5 recycling runs without activity loss) and extensive substrate applicability (12 kinds of olefins) in heterogeneous hydroformylation of olefins with CO 2 , surpassing all homogeneous and heterogeneous catalysts that only contain Rh P sites (Table 5). Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc. ) were employed to get insights into this effective strategy to rationally design efficient single site catalysts.
研究领域:
催化
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材料科学
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化学反应工程
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无机化学
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绿色化学
✓ 已验证
产品关联
DOI
高影响因子
Nature Catalysis
·
2022
·Vol. 5
·期 6
·564-570
·
IF 40.706
Xie Yi,Ou Pengfei,Wang Xue,Xu Zhanyou,Li Yuguang C.,Wang Ziyun,Huang Jianan Erick,Wicks Joshua,McCallum Christopher,Wang Ning,Wang Yuhang,Chen Tianxiang,Lo Benedict T. W.,Sinton David,Yu Jimmy C.,Wang Ying,Sargent Edward H.
Renewable electricity-powered CO 2 reduction to multi-carbon (C 2+ ) products offers a promising route to realization of low-carbon-footprint fuels and chemicals. However, a major fraction of input CO 2 (>85%) is consumed by the electrolyte through reactions with hydroxide to form carbonate/bicarbonate in both alkaline and neutral reactors. Acidic conditions offer a solution to overcoming this limitation, but also promote the hydrogen evolution reaction. Here we report a design strategy that suppresses hydrogen evolution reaction activity by maximizing the co-adsorption of CO and CO 2 on Cu-based catalysts to weaken H* binding. Using density functional theory studies, we found Pd–Cu promising for selective C 2+ production over C 1 , with the lowest ∆ G OCCOH* and ∆ G OCCOH* - ∆ G CHO* . We synthesized Pd–Cu catalysts and report a crossover-free system (liquid product crossover <0.05%) with a Faradaic efficiency of 89 ± 4% for CO 2 to C 2+ at 500 mA cm −2 , simultaneous with single-pass CO 2 utilization of 60 ± 2% to C 2+ .
研究领域:
化学工程
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电化学
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可再生能源
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
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2021
·
IF 7.132
Ye Qu,Yanglin Chen,Jianmin Sun
CO 2 utilization plays an important role in rational use of carbon resources and reduction of carbon emissions. It is still a challenge to achieve efficient CO 2 utilization by amino acid ionic liquids (AAILs) under room temperature and atmospheric pressure with cocatalyst- and solvent-free conditions. Herein, the newly developed AAILs including 1,1,3,3-tetramethylguanidine cation ([HTMG] + ) together with both amino acid and halogen as anions, were simply synthesized by neutralization reaction. Under mild conditions (30 °C, 20 h and 1 MPa CO 2 ), the cycloaddition reaction of CO 2 and propylene oxide could be efficiently catalyzed by [HTMG][His][I] with 99 % propylene carbonate yield and selectivity in the absence of additional solvent and cocatalyst. Notably, even at room temperature and atmospheric pressure for 72 h, [HTMG][His][I] also displayed 96 % yield and 99 % selectivity due to the cooperation of [HTMG] + , [His] 2– and [I] – . Meanwhile, [HTMG][His][I] performed excellent universality of various epoxides and reusability. Based on the characterization results of 1 H and 13 C NMR, it was verified that propylene oxide and CO 2 were simultaneously activated by the functional groups in [HTMG][His][I]. Hence, the reaction mechanism for CO 2 cycloaddition with epoxide catalyzed by [HTMG][His][I] was proposed. This work provided a simple strategy to prepare sustainable AAILs for efficient CO 2 utilization under very mild conditions of room temperature and atmospheric pressure (even the low CO 2 concentration at simulated flue gases).
研究领域:
化学
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环境科学
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材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2025
·
IF 4.3
Longxiangyu Cheng,Zuwei Xu,Haibo Zhao
To address the trade-off between CO 2 conversion and methanol selectivity inherent in Cu-ZnO based catalysts and mitigate the drawbacks of wet chemical synthesis methods, in this study, Cu/ZnO/Al 2 O 3 catalysts with high methanol selectivity were developed for CO 2 hydrotreating to methanol using a mechanochemical method suitable for industrial scale preparation. Combining CuO and ZnO precursors of different sizes (micronscale or nanoscale), four catalyst variants were prepared by a mechanochemical method combining ball milling and auto-combustion of citric acid, which compared with commercial catalyst prepared by co-precipitation method. Characterizations of the catalysts structure and element distribution indicate that due to the different thermal decomposition kinetics of copper citrate and zinc citrate during the calcination process, the surface Zn content of the ball milling catalysts significantly increase, thereby promoting the formation of the Cu-ZnO x interface. Among them, the catalyst of plain CuO + nano ZnO shows the best performance (0.4 g MeOH •g cat -1 •h −1 ). Although its CO 2 conversion is lower than that of commercial catalyst, it has better methanol selectivity and produced higher methanol space–time yield which remained stable during the 30 h stability test. In addition, H 2 -TPR and CO 2 -TPD experimental results show that although mechanical mixing resulted in ball milling catalysts with large copper grains, more oxygen vacancies and moderately strong basic sites enhanced Cu-ZnO synergism, inhibited the reverse water–gas shift (RWGS) reaction, and facilitated methanol synthesis.
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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可持续能源
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CO2利用
✓ 已验证
产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·10497
·
IF 15.7
Wang Zhijie,Zhou Yimian,Ni Wenkang,Li Jianfei,Yue Xuanyu,Zhang Zizhong,Dai Wenxin,Fu Xianzhi
Cu-based nanocatalysts hold promise for the reverse water–gas shift (RWGS) reaction. However, irreversible sintering of the Cu catalyst for deactivation remains a persistent challenge under thermal or photothermal processes. In this study, we develop an anti-sintering catalyst using CuNiMgAl layered-double-hydroxide (LDH)-derived hydroxyl engineering to anchor ultrafine CuNi nanoparticles, achieving stable photothermal RWGS conversion. For Cu 3 Ni-MA, the oxyphilic Ni dopants facilitate the formation of hydroxyl-coordinated Cu 2+ –Ni 2+ species during the calcination of LDH-derived materials; meanwhile, the Ni incorporation enhances the plasmonic effect of CuNi nanocatalysts to drive H 2 spillover for hydroxyl replenishment under light irradiation, which is diverged from conventional Cu 3 Ni alloy-based catalysts. This Cu 3 Ni-MA achieves a CO production rate of 339.8 mmol g −1 h −1 with 98% selectivity, outperforming thermal catalysis by 3.5-fold in RWGS conversion. Notably, the catalyst exhibits robust photothermal CO 2 hydrogenation stability, preserving >99% of its original activity and CO selectivity during 30 d of intermittent start–stop cycles and 280-h continuous testing. This study offers alternative perspectives for designing anti-sintering catalysts for photothermal catalytic systems by coupling dynamic hydroxyl regulation with plasmonic activation mechanisms.
研究领域:
催化
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材料科学
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光热转换
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CO2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
PubMed
高影响因子
CERAMICS INTERNATIONAL
·
2025
·
IF 5.6
Kai Ma,Yao Luo,Jietao Wang,Xu Chang,Tong Liu,Yao Wang,Mingyue Ding
Developing robust fuel electrodes with high catalytic activity and stability under CO/CO 2 atmospheres is critical for reversible solid oxide fuel cells (RSOFCs). Here, we report a novel A-site-deficient perovskite Sr 1.95 Fe 1.5 Mo 0.3 Ni 0.2 F 0.1 O 6-δ (SFMNF) synthesized via electrospinning, combining Ni 2+ (B-site cation) and F - (anion) co-doping to enhance CO 2 electrolysis and syngas oxidation performance. Physicochemical characterization reveals that F-doping lowers the crystallization temperature, increases oxygen vacancy concentration, and strengthens CO 2 chemisorption. Reduction under H 2 induces exsolution of Ni 3 Fe alloy nanoparticles. The SFMNF electrode achieves a current density of 233 mA cm -2 at 1.3 V and 750°C in CO:CO 2 =2:1 atmosphere, with 36.2% higher activity than the pre-reduced state. Electrochemical impedance and distribution of relaxation time analyses identify CO 2 adsorption/dissociation as the rate-limiting step. The cell demonstrates exceptional durability over 50 redox cycles and 85-hour of operation without carbon deposition. This work highlights dual doping as an effective strategy to tailor perovskite properties for efficient CO 2 utilization in RSOFCs.
研究领域:
能源材料
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电化学
·
催化
·
纳米技术
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固体氧化物燃料电池
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CO2利用
✓ 已验证
DOI
高影响因子
FUEL
·
2025
·
IF 7.5
Ziwen Hao,Yabin Li,Yutong Pan,Xiaoyu Han,Qiang Wang,Maoshuai Li,Yue Wang,Xinbin Ma
Interaction between metal species and support affects the structural and electronic properties of metal species, thus changing the catalytic behaviour. This work demonstrates regulation of support size is an effective way to optimise the metal-support interaction over Ni/CeO 2 -cube. Smaller ceria cubes promoted formation of smaller Ni particle sizes with higher dispersion, generating stronger interaction between Ni and CeO 2 , and consequently higher turnover frequency for CO 2 methanation. The interaction in Ni/CeO 2 with the smallest ceria size (average ca. 5 nm) provides stronger CO 2 and H 2 adsorption capacity, facilitating the CO 2 methanation with over 99 % CH 4 selectivity at 548–573 K, delivering a CO 2 conversion rate of 327.9 mol CO2 mol Ni -1 h −1 , which is 1.9 and 14.0 times than that of the 12 nm and 20 nm counterparts at 573 K, respectively. In-situ FTIR spectroscopic analysis demonstrates the surface reaction proceeds via a formate pathway, and smaller CeO 2 -cube supported Ni facilitates conversion of carbonate/bicarbonate intermediates to formate species. The metal-support interaction aroused from controlled support size provides a new way to design high-performance methanation catalyst.
研究领域:
催化化学
·
材料科学
·
多相催化
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CO2利用
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纳米材料
✓ 已验证
产品关联
DOI
高影响因子
ACS Catalysis
·
2019
·
IF 12.221
Wenhui Li,Guanghui Zhang,Xiao Jiang,Yi Liu,Jie Zhu,Fanshu Ding,Zhongmin Liu,Xinwen Guo,Chunshan Song
Cobalt catalysts supported on TiO2 with different crystal forms (anatase and rutile) differ sharply in CO2 conversion and product selectivity for CO2 hydrogenation. The Co/rutile-TiO2 catalyst selectively catalyzed CO2 hydrogenation to CH4, while CO is the main product on the Co/anatase-TiO2 catalyst. In situ DRIFT (diffuse reflectance infrared Fourier transform) results have partially revealed the reaction pathway of CO2 hydrogenation on these two catalysts. On Co/rutile-TiO2, the reaction proceeds through the key intermediate formate species, which is further converted to CH4. Differently, the reaction on Co/anatase-TiO2 undergoes CO2 → *CO, which desorbs to form gas-phase CO instead of subsequent hydrogenation. The strongly bonded *CO is required to enhance the subsequent hydrogenation. By simply changing the calcination temperature of anatase TiO2, the product selectivity can be tuned from CO to CH4 with a significant increase in CO2 conversion due to the surface phase transition of the anatase to the rutile phase. The addition of Zr, K, and Cs further improves the CO, CO2, and H2 adsorption in both the capacity and strength over anatase- and rutile-supported catalysts. The Zr modification makes the reaction pathway over anatase-supported catalyst proceed via the intermediate formate species and enables the subsequent hydrogenation to CH4. In addition, the surface C/H ratio increases significantly in the presence of promoters (unpromoted < Zr-promoted < K-Zr-promoted ∼ Cs-Zr-promoted), which leads to the highest C2+ selectivity of 17% with 70% CO2 conversion over K-Zr-Co/anatase-TiO2 catalyst. These results reveal mechanistic insights into how the product distribution of Co/TiO2 catalysts can be manipulated through adjusting the adsorption performance and surface C/H ratio.
研究领域:
催化化学
·
材料化学
·
多相催化
·
CO2利用
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表面科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）