CERAMICS INTERNATIONAL
·
2024
·
IF 5.1
Jie Zhang,Chenhui Qiu,Lei Wang,Ruijie Chen,Jing Ding,Jinfeng Zhang,Hui Wan,Guofeng Guan
Photocatalytic CO 2 reduction presents a promising strategy to alleviate environmental issues caused by massive CO 2 emissions. SrTiO 3 , a potential photocatalyst for photocatalytic CO 2 reactions, is limited by poor photoresponsivity and fast photogenerated carrier recombination. In this work, a series of Cu 2+ species modified SrTiO 3 nanofibers (xCuO/STO) was prepared combining sol-gel method and electrospinning with different copper content. The CH 3 OH yield of the 0.08CuO/STO photocatalyst reached up to 5.75 ± 0.27 μmol g −1 h −1 , which was 2.2 times higher than that of pure SrTiO 3 . It was attributed that the blend electrospinning promoted Cu 2+ species to be well dispersed on the surface of the SrTiO 3 nanofibers. The strategy effectively enhanced the light absorption of the photocatalyst and inhibited the recombination of the photogenerated carriers. Part of appropriate characterizations were employed to elucidate the above point. In addition, to explore the inherent mechanism between the two species, the Density Functional Theory (DFT) calculations were further applied in the inherent mechanism between the species. This work provided a blend electrospinning approach for designing cocatalyst-modified SrTiO 3 nanofibers for photocatalytic reduction of CO 2 .
研究领域:
材料科学
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环境科学
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化学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
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2023
·
IF 22.1
Minzhi Ma,Zeai Huang,Lina Li,Wenda Zhang,Rui Guo,Ruiyang Zhang,Wenjun Fa,Chunqiu Han,Yuehan Cao,Shan Yu,Ying Zhou
The performance of photocatalytic reduction CO 2 to CH 3 OH is intimately tied to the photogenerated electron density of the active center, because CH 3 OH formation involves a 6-electron transfer process. However, the random migration of photocarriers in the photocatalysts is severely not conducive to the directional delivery and enrichment of photogenerated electrons to active sites, leading to poor photocatalytic activity for CO 2 to CH 3 OH. Herein, we reported a coordination environment engineered Pr single-atom catalyst for boosting the photogenerated electron density of the active sites, achieving the high-efficiency photoreduction of CO 2 to CH 3 OH. The carbon nitride (CN) supported Pr single-atom with oxygen coordination was designed via a three-step pyrolysis process . Then, the engineered oxygen coordination configuration for the Pr single-atom (Pr 1 -N 4 O 2 ) was successfully achieved. Importantly, this Pr 1 -N 4 O 2 sites can induce photogenerated electrons more easily to accumulate on the Pr atom as compared to the reference catalyst of the Pr atom without oxygen coordination (Pr 1 -N 6 ). Moreover, the formed atomically dispersed Pr 1 -N 4 O 2 active centers with ultra-high Pr loading (21.05 wt%) can promote CO 2 adsorption and activation, and provide a high density of active sites for CO 2 photoreduction. As a result, the optimized Pr 1 -N 4 O 2 /CN exhibited a boosted photoreduction of CO 2 to CH 3 OH activity (511.1 μmol g −1 h −1 ), which was up to 28.9 and 1.9 times higher than those of CN (17.7 μmol g −1 h −1 ) and Pr 1 -N 6 /CN (274.1 μmol g −1 h −1 ), and preferable to most reported work under similar catalytic conditions. Our findings can provide a fresh prospect for developing innovative SACs to enhance the photoreduction of CO 2 to CH 3 OH activity.
研究领域:
材料科学
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催化
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环境化学
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光化学
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产品关联
DOI
高影响因子
ACS Omega
·
2018
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IF 0
Zhongwei Fu,Yunyun Zhong,Yuehong Yu,Lizhen Long,Min Xiao,Dongmei Han,Shuanjin Wang,Yuezhong Meng
A new class of TiO2-doped CeO2 nanorods was synthesized via a modified hydrothermal method, and these nanorods were first used as catalysts for the direct synthesis of dimethyl carbonate (DMC) from CO2 and CH3OH in a fixed-bed reactor. The micromorphologies and physical–chemical properties of nanorods were characterized by transmission electron microscopy, X-ray diffraction, N2 adsorption, inductively coupled plasma atomic emission spectrometry, X-ray photoelectron spectroscopy, and temperature-programmed desorption of ammonia and carbon dioxide (NH3-TPD and CO2-TPD). The effects of the TiO2 doping ratio on the catalytic performances were fully investigated. By doping TiO2, the surface acid–base sites of CeO2 nanorods can be obviously promoted and the catalytic activity can be raised evidently. Ti0.04Ce0.96O2 nanorod catalysts exhibited remarkably high activity with a methanol conversion of 5.38% with DMC selectivity of 83.1%. Furthermore, kinetic and mechanistic investigations based on the initial rate method were conducted. Over the Ti0.04Ce0.96O2 nanorod catalyst, the apparent activation energy of the reaction was 46.3 kJ/mol. The reaction rate law was determined to be of positive first-order to the CO2 concentration and the catalyst loading amount. These results were practically identical with the prediction of the Langmuir–Hinshelwood mechanism in which the steps of CO2 adsorption and activation are considered as rate-determining steps.
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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环境化学
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DOI
PubMed
RSC Advances
·
2014
·Vol. 4
·期 54
·28683-28690
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IF 3.708
Jie Feng,Zhifei Wang,Bin Shen,Liming Zhang,Xia Yang,Nongyue He
Mesoporous silica-coated Au nanorods (Aurod@SiO2) have recently attracted considerable interest in nanomedicine, and the template removal procedure is crucial for the preparation of such hybrid nanostructure. Herein, two kinds of typical extraction solvents, i.e., NH4NO3–CH3OH and HCl–CH3OH, were separately used to extract the surfactant cetyltrimethylammonium bromide (CTAB) from the obtained Aurod@SiO2. The results show that CTAB molecules could be completely removed from the pores of Aurod@SiO2 without damaging the internal Au nanorod by NH4NO3–CH3OH, while Aurod@SiO2 treated with HCl–CH3OH suffered from both poor extraction efficiency and the shape transformation of Au nanorod due to selective etching in the presence of oxygen. In addition, the consequent drug loading experiment shows that Aurod@SiO2 extracted by NH4NO3–CH3OH possesses a larger drug loading capacity with a loading efficiency of 82.5%. Furthermore, the in vitro photo-thermal therapy experiment shows that Aurod@SiO2 extracted by NH4NO3–CH3OH is more efficient in killing the YCC-2 gastric cancer cells as compared with that extracted by HCl–CH3OH.
研究领域:
纳米医学
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材料科学
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生物医学工程
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癌症研究
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产品关联
DOI
高影响因子
Nature Communications
·
2025
·Vol. 16
·期 1
·1-13
·
IF 15.7
Zhang Xiuming,Jiang Yuheng,Gu Hongfei,Zhang Haoqing,Li Yuemei,Lu Zexuan,Zhang Shuping,Liu Jia,Zhang Jiatao,Tang Zhiyong
The direct oxidation of methane into methanol exploiting O 2 as oxidant offers an ideal route for methane utilization. Although the reaction is strongly preferred in thermodynamics, conventional catalytic systems always demand intense energy input like high temperatures or high-energy photons (>2.8 eV) to conquer the large kinetic barrier in the conversion process. In this study, we demonstrate that by creation of a suitable plasmonic photocatalyst, namely oxygen-vacancy-rich CuSeO 3-x , the low-energy near-infrared (NIR) photons can serve as the sole energy input to complete CH 4 -to-CH 3 OH conversion with remarkable activity (Apparent quantum yield of 1.5% at 800 nm with Au cocatalyst) and near unity selectivity (ca. 96%) at 25 °C. Such fascinating performance is attributed to a small activation energy measured at 0.28 eV, enabled by the existence of Cu II -O v species in CuSeO 3-x . Our study suggests that the ensemble of Cu II -O v constitutes an exceptional active site, which can harness the plasmon-induced hot electrons and meantime brings a kinetically advantageous route for reducing O 2 into •OH radicals greatly favoring methane activation.
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产品关联
DOI
PubMed
高影响因子
DOKLADY PHYSICAL CHEMISTRY
·
2025
·Vol. 520
·期 1
·1-10
·
IF 1.5
Xingbing Yang,Zhang Tingting,Zhu Jing,Wu Qian,Zhang Qin,Li Jingyi,Jiang Tingting,Xiao Qin
In this work, the isothermal solution equilibrium method was used to examine the phase equilibrium of a ternary LiCl–LiBr–CH 3 OH system at 273 and 323 K. The solubilities of LiCl and LiBr in CH 3 OH at different temperatures were measured by chemical analysis. The chemical composition of the equilibrium solid phase was determined via the wet slag method combined with X-ray diffraction. Thus, the corresponding phase diagram was created, and the LiCl–LiBr–CH 3 OH and LiCl–LiBr–H 2 O ternary systems were compared at different temperatures. The results showed that the phase diagram characteristics of the LiCl–LiBr–CH 3 OH ternary system at 273 and 323 K were similar, with a saturation point, two univariable solubility curves and two solid phase crystallization zones; these zones represented the Li(Cl,Br) solid solution crystallization zone and LiCl single salt crystallization zone. The single salt of LiCl can be separated using crystallization filtration. LiBr has a salt-out effect on LiCl, but LiBr cannot be obtained. With increasing temperature, the contents of LiCl and LiBr at the saturation point of the LiCl–LiBr–CH 3 OH ternary system increase, and the solubilities of LiCl and LiBr in methanol gradually increase.
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Pengchao Ren,Weifeng Tu,Chanchan Wang,Sifan Cheng,Wenqi Liu,Zhenzhou Zhang,Yun Tian,Yi-Fan Han
This study investigated the Cu-CeO 2 interactions for CO hydrogenation to methanol by applying rate measurements, chemical titration/desorption, together with in-situ/operando spectroscopy techniques under realistic reaction conditions. Ce components were enriched in the surface region of Cu/CeO 2 catalysts while Ce 3+ and Ce 4+ atoms co-existed during CO hydrogenation. The ratio of Ce 3+ to Cu 0 in the surface region of catalysts increased linearly with the Ce content. The turnover rates of CH 3 OH formation increased as a single-valued function of the ratio, irrespective to the individual contact extent between Cu and CeO 2 clusters or Ce content in the Cu/CeO 2 catalysts, indicating that the Cu 0 -Ce 3+ sites pair acts as active sites for CO hydrogenation to methanol over Ce-CeO 2 samples. This study also unraveled that formyl and formate species, as reactive surface intermediates, were co-adsorbed on the Cu 0 -Ce 3+ sites, and their hydrogenation routes occurred concurrently for CH 3 OH formation during CO-H 2 reactions.
研究领域:
催化
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化学工程
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表面科学
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2021
·
IF 19.503
Yamei Huang,Peiyao Du,Wen-Xiong Shi,Ye Wang,Shuang Yao,Zhi-Ming Zhang,Tong-Bu Lu,Xiaoquan Lu
Solar-driven CO 2 reduction with H 2 O oxidation into liquid fuels is highly desirable for sustainable carbon cycle to achieve carbon neutral, but represents a great challenge for artificial photosynthesis. Herein, bimetallic PdIn nanoclusters are confined in a photosensitizing covalent organic framework (N 3 -COF) to facilely construct Pd x In y @N 3 -COF composites (x:y = 1:0, 0:1, 1:2, 1:1, 2:1). The resulting PdIn@N 3 -COF exhibits excellent activity for CO 2 photoreduction with H 2 O oxidation as the H + and e − source, showing a record-high total yield of 798 μmol g -1 for producing CH 3 OH (74 %) and CH 3 CH 2 OH (26 %) among the framework materials. The synergy in both the bimetallic nanocluster and cluster@N 3 -COF contributes greatly to C C coupling and interfacial charge transfer, thus achieving excellent activity for conversion of CO 2 to C 1 /C 2 alcohols on the non-copper catalysts. This work highlights the amazing potential for constructing bimetallic nanocluster@photosensitizing supports to produce alcohols in artificial photosynthesis with H 2 O oxidation.
研究领域:
材料科学
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化学
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环境科学
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能源科学
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产品关联
DOI
高影响因子
Journal of Environmental Chemical Engineering
·
2025
·Vol. 14
·期 1
·120722
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IF 7.2
Changming Zhang,Wensheng Wu,Lingzhi Huang,Jiangxiu Liang,Xiaochao Zhang,Xiushuai Guan,Jinbo Xue
Photocatalytic reduction of CO 2 to CH 3 OH is a promising strategy for the conversion of high value-added chemicals, and it is particularly important to overcome the serious problem of multiproton electronic coupling process. In this paper, we promoted the adsorption of CO 2 and the selectivity of the reduction products by modulating the presence form and the number of active sites of palladium on hierarchical porous carbon spheres. The Pd x -modified carbon spheres exhibited excellent CO 2 adsorption performance (2.17 mmol g −1 ) and photocatalytic reduction activity (CO yield of 14.35 μmol g −1 , CH 3 OH yield of 0.192 mmol L −1 ) while the loading amount of Pd was 0.05 at%, and the yields of the liquid-phase products can still remain around 97.3 % after ten cycles. The analysis results showed that the introduced Pd mainly consisted of 0-valent and + 2-valent states, and the proportion of + 2-valent Pd had a good correlation with the CH 3 OH yield. It was suggested that the + 2-valent Pd and pyridine nitrogen were the main active species and reaction sites. On one hand, pyridine nitrogen played an important role in improving the adsorption and activation of CO 2 , and promoting the reaction of H + with CO 2 to form COOH*. On the other hand, the introduction of Pd active sites not only significantly enhanced the transfer of electrons and holes, but also improved the generation of key intermediates for the conversion of CH 3 OH. This study will provide a new perspective for the design of highly selective photocatalysts.
研究领域:
材料科学
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光催化
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环境化学
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碳材料
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可持续能源
✓ 已验证
产品关联
DOI
高影响因子
Nature 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
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催化
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材料科学
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理论化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Environmental Chemical Engineering
·
2024
·
IF 7.4
Xiangqian Guo,Chenhui Qiu,Zhiqiang Zhang,Jie Zhang,Lei Wang,Jing Ding,Jinfeng Zhang,Hui Wan,Guofeng Guan
Photocatalytic CO 2 reduction plays an important role in solving environmental issues and alleviating the energy crisis. However, it is still challenging to distribute the surface-active site on photocatalysts with efficient separation of carriers in rational. Herein, the Cu species loaded SrTiO 3 nanofiber was constructed through coaxial electrospinning which could realize the dispersion of the Cu site on the one-dimensional (1D) nanofiber structure. The 1D nanofiber with Cu site exhibited superior performance on photocatalytic CO 2 reduction based on the excellent ability of charge separation. The Cu 2 O and CuO were determined to be located on the surface of 1D SrTiO 3 nanofiber by the TEM and XPS. The work functions of SrTiO 3 , Cu 2 O, and CuO were calculated to be 5.26, 5.47, and 5.51 eV, respectively, suggesting that the carriers could transfer from SrTiO 3 nanofiber to the Cu species. The yield of CH 3 OH with the optimized 8%Cu-SrTiO 3 catalyst could reach 8.08 ± 0.03 µmol⋅g −1 ⋅h −1 . This work provided a coaxial electrospinning strategy to load the Cu species active site on the surface of 1D SrTiO 3 nanofiber for enhancing photoreduction CO 2 .
研究领域:
材料科学
·
环境科学
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能源科学
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纳米技术
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产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2020
·
IF 16.683
Xianying Wang,Yingshu Wang,Meichao Gao,Jinni Shen,Xipeng Pu,Zizhong Zhang,Huaxiang Lin,Xuxu Wang
Construction of composite semiconductors is an effective solution to elevate the efficiency of photocatalysis by prolonging lifetime of photogenerated hole and electrons. Herein, a heterojunction structure composite BiVO 4 /Bi 4 Ti 3 O 12 was synthesized via a facile in situ hydrothermal condition. The novel composite photocatalyst has excellent photocatalytic ability to reduce CO 2 with H 2 O into CH 3 OH and CO. The BiVO 4 /10 % Bi 4 Ti 3 O 12 sample shows the highest yields of CH 3 OH and CO up to 16.6 and 13.29 μmol g −1 h −1 , which was 12.39 and 5.68 times higher than that of pure BiVO 4 , and 9.88 and 2.80 times higher than that of pure Bi 4 Ti 3 O 12 , respectively. Such a high activity is attributed to the type II heterojunction structure which significantly enhances separation of photogenerated carriers and promotes collaboration between the water oxidation on the Bi 4 Ti 3 O 12 and the CO 2 reduction on BiVO 4 . The photocatalytic reaction mechanism of CO 2 on the composite was proposed according to experiment results.
研究领域:
材料科学
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环境科学
·
化学工程
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）