ACS Sustainable Chemistry & Engineering
·
2025
·
IF 7.3
Yan Shao,Jun Wan,Xiaoxia Ou,Cui Quan,Ningbo Gao,Xin Wang,Feng Zeng,Rongsheng Cai,Xiaolei Fan,Huanhao Chen
Engineering Pd–In2O3 interaction is key to developing catalysts with the desired CO2 hydrogenation activity toward methanol synthesis. Here, the crystalline phase of In2O3 nanospheres was tuned by changing the calcination temperature, which was found to affect the Pd–In2O3 interaction and thus the supported Pd states and CO2 hydrogenation performance of the prepared Pd/In2O3-a catalysts (where a refers to the calcination temperature for preparing In2O3). The fresh Pd/In2O3-a catalysts show varied initial activities, and after the induction period, their performance stabilized though being different. During the 100 h catalysis, catalyst microstructures changed, showing Pd aggregation and Pd–In alloying, which was related to the nature of the crystalline phase of In2O3. The hexagonal (h-In2O3) phase in Pd/In2O3-400 possesses concentrated surface OH groups and limited mobility. The relatively poor mobility limits Pd–In alloying, which possibly suppresses the hydrogen spillover effect, causing low CO2 conversion (8%) and methanol selectivity (45%) under steady-state conditions at 5 MPa and 300 °C. Conversely, the cubic In2O3 (c-In2O3) phase promotes Pd–In alloying and modifies Pd–In2O3 interaction during the reaction. The activity data show that Pd/In2O3-600 with the mixed phases of In2O3 (h/c-In2O3) demonstrated appropriate Pd–In2O3 interaction, leading to the Pd core InOx shell structure with the comparatively best methanol selectivity of about 65% at steady state. Conversely, Pd/In2O3-800 with the pure cubic In2O3 (c-In2O3) phase and a relatively low specific surface area of 16 m2 g–1 encourages the sintering of Pd and thereby the formation of homogeneous Pd–In alloys, having a moderate methanol selectivity of about 50%. These findings highlight the importance of the In2O3 crystal phase engineering in the catalytic CO2 hydrogenation over Pd/In2O3 catalysts and the dynamics of Pd–In interactions, which affect the methanol yield.
研究领域:
催化化学
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材料科学
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能源化学
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产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2022
·
IF 7.392
Zhuping Li,Yong Men,Shuang Liu,Jinguo Wang,Keye Qin,Dandan Tian,Tianle Shi,Li Zhang,Wei An
The crystalline phases of support have great influence on their surface and structure properties. Therefore, adjusting the crystalline structure of heterogeneous catalysts imposes a significant impact on the catalytic performance. Herein, a suite of Pd/In 2 O 3 /ZrO 2 catalysts with different crystalline phases of ZrO 2 were prepared and evaluated for CO 2 hydrogenation to CH 3 OH using the same amount of metal loading. The activity data showed the distinct superior reactivity of Pd/In 2 O 3 /ZrO 2 catalyst used mixed monoclinic and tetragonal phases ZrO 2 (Mix-ZrO 2 ) as support as compared to respective single phase of monoclinic ZrO 2 (m-ZrO 2 ) and tetragonal ZrO 2 (t-ZrO 2 ). The catalysts are extensively characterized through BET, XRD, HRTEM, UV–vis, H 2 -TPR, CO 2 /H 2 -TPD and XPS. Combining the characterization results and activity data, the superior activity of Pd/In 2 O 3 /Mix-ZrO 2 catalyst can be correlated with large particle size of Pd nanoparticles, the concentration of oxygen vacancies, and the abundant medium basic sites, which were essential for activation of H 2 and inert CO 2 and enhancement of catalytic performance. The best-performing Pd/In 2 O 3 /Mix-ZrO 2 catalyst exhibited a remarkable reactivity with space time yield (STY) of 0.54 g methanol ·h −1 ·g cat −1 at 573 K and 5 MPa, and stability without noticeable deactivation after 100 h of time on stream, demonstrating its potential as catalyst used in CH 3 OH synthesis from CO 2 hydrogenation.
研究领域:
催化化学
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材料科学
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能源化学
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产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2024
·
IF 6.5
Qiang Zhou,Xinyu Wang,Tao Xing,Mingqing Wang,Mingbo Wu,Wenting Wu
Hydrogen peroxide (H 2 O 2 ) is widely used as an oxidant for photocatalytic oxidation of methane to value-added chemicals under mild conditions, but suffers from low utilization efficiency. Herein, we propose a comprehensive strategy for the proper amount of hydroxyl radicals (•OH) generation from H 2 O 2 by regulating the Pd/Au molar ratios and the total Au-Pd contents loaded on In 2 O 3 . For the photocatalytic oxidation of methane at ambient temperature, the yield and selectivity of CH 3 OH over the optimized 1.0% AuPd 0.5 /In 2 O 3 catalyst were as high as 2187.0 μmol g −1 h −1 and 94.0% respectively, exceeding most reported literatures. Mechanism investigations revealed that the formation of Au-Pd alloys may contribute to the homolytic cleavage of H 2 O 2 into •OH radicals and improve the selectivity of •OH generation. This work provides some guidance for the delicate design of photocatalysts to manipulate selective H 2 O 2 activation and efficient photocatalytic methane oxidation.
研究领域:
化学
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催化
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环境科学
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材料科学
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产品关联
DOI
高影响因子
ACS Catalysis
·
2021
·
IF 13.084
Zhongjie Cai,Meng Huang,Jiajun Dai,Guowu Zhan,Fu-li Sun,Gui-Lin Zhuang,Yiying Wang,Pan Tian,Bin Chen,Shafqat Ullah,Jiale Huang,Qingbiao Li
Methanol synthesis from CO2 hydrogenation with H2 produced from renewable energy has emerged as a promising method for carbon neutrality. The supported Pd/In2O3 catalyst has attracted great attention due to its superior activity and methanol selectivity, but the formation of the In–Pd bimetallic phase upon over-reduction would lead to quick catalyst deactivation. In this work, we elucidate the reduction behavior of Pd/In2O3 catalysts by using TCPP(Pd)@MIL-68(In) as precursors. During catalyst fabrication, metalloporphyrins (viz., TCPP(Pd)) served as both a capping agent for the growth of MIL-68(In) and a shuttle for transporting the Pd2+, which enhanced the dispersion of Pd0 species on In2O3–x during the calcination and reduction treatments and prevented the formation of In–Pd bimetallic phase by over-reduction. With a low Pd loading of 0.53 wt %, the resultant Pd/In2O3 catalyst exhibited a maximum methanol space–time yield of 81.1 gMeOH h–1 gPd–1 with a CO2 conversion of 8.0% and a methanol selectivity of 81% over 50 h on stream (295 °C, 3.0 MPa, 19,200 mL gcat–1 h–1). In contrast, the comparative Pd/In2O3 catalyst prepared by the impregnation of PdCl2 in MIL-68(In) showed poor activity and stability due to the formation of InPd/In2O3–x surface structures. In addition, we found a strong connection between the reduced degree of In2O3 and the catalytic performance of the supported Pd/In2O3 catalysts by integrating catalyst characterization results with density functional theory (DFT) calculations. Interestingly, the surface In/O ratio detected by XPS can reflect information about both metal–support interaction and the amount of oxygen vacancy, which is highly related to the catalytic activity. The DFT calculation also shows that the Pd/In2O3 catalyst has excellent thermodynamic selectivity for the CH3OH product. This work provides an alternative synthetic strategy for Pd/In2O3 nanocatalysts and sheds light on the deactivation mechanism of the supported catalysts.
研究领域:
催化化学
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材料科学
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环境科学
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产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2022
·
IF 9.136
Kok Bing Tan,Pan Tian,Xinxin Zhang,Jian Tian,Guowu Zhan,Jiale Huang,Qingbiao Li
The present study developed bifunctional catalyst for CO 2 hydrogenation into dimethyl ether (DME), whereby it consists of Pd/In 2 O 3 for CO 2 hydrogenation into methanol, and H-ZSM-5 for methanol dehydration into DME. The catalyst development was focused on the synthesis of Pd/In 2 O 3 via a green and low-cost synthesis method of carbonized alginate templating. Thus, microspherical-confined nano-Pd/In 2 O 3 was formed, whereby the localized nucleation growth was coordinated by the chemically entrapped In 3+ via ionic bond in the well-distributed alginate structure. It was found that hydrothermal temperature plays a key role in the development of this catalyst structure. The optimum hydrothermal temperature is 160 °C, as it is able to produce the highest amount of methanol. This catalyst was further integrated with H-ZSM-5 via different integration manners. It was found that mortar mixed method produces the highest amount of DME, as the close proximity causes stronger ion-exchange mechanism between the catalyst components, which facilitates higher oxygen vacancy density in the bifunctional catalyst. Under the optimum Pd/In 2 O 3 : H-ZSM-5 (PdIn-160–12: H-ZSM-5) mass ratio of 4:1, the highest STY DME of 79.7 g DME kg cat -1 h −1 with CO 2 conversion of 9% and DME selectivity of 44.1% can be achieved. In addition, the STY DME can be maintained even in 60 h on stream, demonstrating the excellent stability and performance of microspherical-confined nano-Pd/In 2 O 3 /H-ZSM-5 bifunctional catalyst synthesized via carbonized alginate templating strategy.
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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能源科学
✓ 已验证
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
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IF 13.2
Xin Song,Mingyi Li,Jiaqi Xiong,Fangjun Shao,Zhongzhe Wei,Wenjuan Fang,Jianguo Wang
The carboxylation of alkynes with CO 2 is a pivotal reaction in organic synthesis. However, the generally poor adsorption and activation of CO 2 in heterogeneous catalytic systems have become a bottleneck problem restricting the efficiency of carboxylation reactions. In this study, we proposed a strategy for modifying heterogeneous catalysts with ionic liquid. By utilizing amino acid ionic liquids to modify the Pd/In 2 O 3 catalyst, the electronic structure of palladium (Pd) nanoparticles is optimized, and the adsorption and activation of CO 2 on the catalyst is enhanced. Additionally, the h-In 2 O 3 support not only regulates the electronic structure of Pd nanoparticles but also provides abundant oxygen vacancies, which facilitates the adsorption of CO 2 in the system. Due to the synergistic catalytic effects of the amino acid ionic liquid and the oxygen vacancies in the h-In 2 O 3 support, the Pd/h-In 2 O 3 -BmimPro catalyst demonstrates a remarkable phenylpropiolic acid yield of 93 % under mild conditions (50 °C, 0.5 MPa). This study provides valuable insights into the application of ionic liquid-modified catalysts in CO 2 conversion technologies.
研究领域:
催化化学
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有机合成
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二氧化碳利用
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材料化学
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绿色化学
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产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2020
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IF 7.1
Yaxu Zhao,Shaohua Wang,Wenjing Yuan,Shurui Fan,Zhongqiu Hua,Yi Wu,Xuemin Tian
Gas sensors based on In 2 O 3 were prepared and were found to be very sensitive to methane with Pd loading (Pd-In 2 O 3 ), even at a low temperature of 300 °C. However, Pd-In 2 O 3 sensors suffer from a high cross-sensitive response to NO 2 , CO and ethanol, which are typical interfering gases for the detection of CH 4 . In order to promote the selective response to CH 4 , a filter based on Pt-Al 2 O 3 catalyst film was printed onto the top of Pd-In 2 O 3 sensor layer. It was found that catalytic film coated sensors could selectively respond to methane even in the mixture of methane with CO, NO 2 , and ethanol. The cross-sensitive responses to the interference of VOCs, CO, NO 2 were almost eliminated. According to the catalytic conversion measurement, it was indicated that CO and ethanol were fully and selectively oxidized to CO 2 and H 2 O. In case of NO 2 , it was proposed that nitrogen dioxide molecules may be blocked on the surface of the catalyst film. Based on the oxygen adsorption behavior, it was suggested the printed catalyst film has no change on the basic sensing mechanism of In 2 O 3 based sensors following the general model that is the adsorption of oxygen and interaction with methane molecule and the resulted electron transfer process. Our investigation demonstrated that Pt-Al 2 O 3 printed Pd-In 2 O 3 sensor could be used for the detection of CH 4 leakage and monitor.
研究领域:
材料科学
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环境监测
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化学工程
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DOI
高影响因子
ACS Applied Nano Materials
·
2026
·Vol. 9
·期 30
·14188-14198
·
IF 5.8
Qiu Changkun,Zhu Liang,Li Qingrun,Wang Haozhi,An Fei,Wang Shiqiang,Fan Chao,Yang Zhe
Hydrogen
sulfide (H 2 S), a highly toxic and corrosive
gas, requires highly sensitive, selective, rapid, and stable trace-level
detection in various industrial settings. To address the limitations
of conventional metal oxide-based H 2 S sensors─such
as insufficient detection limits, poor selectivity, and inadequate
long-term stability─this study developed an H 2 S
sensor by integrating Pd-loaded In 2 O 3 nanomaterials
with microelectro-mechanical systems (MEMS) technology. A Pd–In 2 O 3 composite with a one-dimensional nanorod structure
was successfully synthesized via a hydrothermal method followed by
thermal treatment. Systematic characterization confirmed that Pd nanoparticles
are uniformly dispersed on the In 2 O 3 surface
in the metallic state. When fabricated into a MEMS-based sensor, the
composite exhibited excellent overall performance at near-ambient
temperature (25 ± 2 ° C): a detection limit as low as 50
ppb, response and recovery times of 8 and 13 s, respectively, a selectivity
ratio ≥5 (response to H 2 S compared to interfering
gases such as CO, H 2 , and CH 4 ), and less than
3% fluctuation in repeated tests. Theoretical calculations revealed
that the adsorption energy of H 2 S on Pd–In 2 O 3 (−0.787 eV) is more negative than that on pristine
In 2 O 3 (−0.679 eV), accompanied by a greater
charge transfer (0.124 |e| vs 0.086 |e| for pristine In 2 O 3 ). Mechanistic analysis indicated that Pd doping not
only modulates the band structure of In 2 O 3 via
an electronic doping effect (forming a Schottky junction) but also
acts as catalytic active sites, preferentially promoting the surface
oxidation of H 2 S. The synergistic effect of enhanced adsorption
affinity, accelerated charge transfer (verified by theoretical calculations),
and selective catalysis significantly improves the sensor’s
sensitivity, selectivity, and response speed. This work provides an
effective strategy for material design and device implementation in
developing high-performance, low-power, and easily integrable trace
H 2 S sensors.
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2024
·
IF 13.3
Qinglei Wu,Chenyang Shen,Kaihang Sun,Menghui Liu,Chang-jun Liu
Tuning the hydrogenation activity of Pd is an effective method to achieve selective hydrogenation of acetylene. The previous study shows that Pd has a strong interaction with In 2 O 3 , causing a significant change in the electronic structure of the palladium catalyst. Herein, Pd/In 2 O 3 @SiO 2 was prepared by a deposition-precipitation method for selective hydrogenation of acetylene. After the reduction by flowing hydrogen, Pd-In intermetallic compounds can be formed. The concentration of the formed intermetallic compounds is closely associated with the reduction temperature. The Pd-In intermetallic compounds suppress the hydrogen activation ability of Pd and significantly weaken the adsorption of ethylene. Especially, a weak adsorption of di-σ-bonded ethylene is observed, which facilitates the desorption of ethylene and promotes the ethylene selectivity in the semi-hydrogenation of acetylene. The experimental study confirms that there exists an optimum reduction temperature (250 °C) for the formation of the Pd-In intermetallic compounds, with which ∼ 80 % ethylene selectivity and 100 % acetylene conversion have been achieved at 140 °C.
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
SENSORS AND ACTUATORS B-CHEMICAL
·
2026
·
IF 8.3
Ertai Na,Binrong Chen,Xudong Liang,Junda Li,Ruifu Ling,Xianbo Zhou,Jiayu Li,Guo-Dong Li
For the early warning of electrical fire, it is of great significance to selectively and timely detect 2-ethylhexanol (2-EH), which is a key gaseous product released from the overheated PVC covered on cables. However, the detection of 2-EH is always hindered due to the weak adsorption and activation ability of the sensing materials. Herein, we constructed dual sites contained Pd-In 2 O 3 sensor for the detection of trace 2-ethylhexanol at ppb level. In this structure, hydroxyl oxygen in 2-EH forms significant bond with In atoms, while alkyl hydrogen generates strong interaction with Pd cluster. As a result, the 0.3 Pd-In 2 O 3 sensor exhibits high response (S = 42 at 11 ppm), low detection limit (0.11 ppm) and short response time (2 s). Band structure analysis reveals that the formation of Schottky junction and spontaneous electron transfer between In 2 O 3 and Pd, leading to the improved gas-sensing performance. This work not only offers new insights into the sensing mechanism by DFT calculations but also paves the way for designing high-performance gas-sensitive materials targeted at complex organic molecules.
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2026
·
IF 9.6
Yinying Shu,Songqi Li,Yuquan Li,Cheng Zheng,Xiaogang Yang,Yahui Cai,Zhengying Wu,Jundie Hu,Jiafu Qu
Interfacial engineering enables Pd 0 /oxygen vacancy balance in Pd/In 2 O 3 . • Hollow In 2 O 3 nanotubes moderate Pd-In 2 O 3 metal-support interaction. • Pd/h-In 2 O 3 achieves 8020 mmol FA mol Pd −1 h −1 for formate production. • Pd 0 retention and defect accessibility jointly govern formate formation. The catalytic performance of oxide-supported Pd catalysts in CO 2 hydrogenation is highly dependent on the interfacial cooperation between metallic Pd 0 sites and defect-containing oxide domains. However, how to regulate this metal-oxide interfacial balance to simultaneously promote H 2 activation and CO 2 -derived intermediate conversion remains insufficiently understood. Herein, we develop an interfacial engineering strategy to regulate the balance between metallic Pd 0 sites and oxygen vacancies (Ov) in Pd/In 2 O 3 catalysts through morphology-dependent metal-support interaction (MSI). Structural analyses reveal that hollow In 2 O 3 nanotubes (h-In 2 O 3 ) effectively moderate Pd-In 2 O 3 interactions, preserve a higher fraction of metallic Pd 0 , and maintain accessible defect-associated oxide domains, thereby establishing a more favorable interfacial configuration than compact counterparts. Consequently, Pd/h-In 2 O 3 delivers the highest formate production rate of 8178 ± 145 mmol FA mol Pd −1 h −1 at 60 °C and 2 MPa, representing a sixfold enhancement over rod-like Pd/In 2 O 3 (Pd/r-In 2 O 3 ), together with excellent stability. These findings highlight that the coordinated regulation of metallic-site preservation and defect accessibility is critical for constructing efficient metal-oxide interfaces for CO 2 hydrogenation to formate. Interfacial engineering optimizes the Pd 0 /Ov balance in Pd/In 2 O 3 by moderating metal-support interaction, enabling high formate productivity (8178 ± 145 mmol FA mol Pd −1 h −1 ) in CO 2 hydrogenation. Download: Download high-res image (147KB) Download: Download full-size image
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Wenxin Liu,Jiabin Zou,Shuni Li,Jinkun Li,Feihu Li,Zili Zhan,Yeguang Zhang
Hydrogen sensors are easily deactivated by hexamethyldisiloxane (HMDSO) poisoning. Moreover, the existing anti-poisoning strategies can also damage the overall sensing performance of these hydrogen sensors. Therefore, a new bilayer design with a Pd/In 2 O 3 sensitive layer and an In 2 O 3 /Al 2 O 3 catalytic filter layer is proposed to avoid the deactivation of hydrogen sensors. The In 2 O 3 /Al 2 O 3 layer helps in hindering HMDSO and its decomposition products from reaching the Pd/In 2 O 3 layer. The H 2 response of the sensors is enhanced due to the small size of In 2 O 3 and the electronic sensitization of Pd. As a result, the bilayer sensors exhibit high response (Ra/Rg = 53) and ultra-fast response time (1 s) towards 3000 ppm H 2 at 365 °C. The resistance and the H 2 response of the bilayer sensors are almost unchanged after 40 min of 10 ppm HDMSO poisoning. In this paper, the mechanism of resistance against silicone poisoning and the H 2 response of the bilayer sensors are discussed from the separation of sensing and catalytic filtration reactions to the behavior of adsorbed oxygen.
研究领域:
材料科学
·
传感器技术
✓ 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）