AICHE JOURNAL
·
2023
·Vol. 69
·期 7
·e18078
·
IF 3.7
Yanping Yang,Jiarui Yang,Shucheng Shi,Yunhong Luo,Xingjun Xu,Yanan Liu,Dianqing Li,Junting Feng
Selective acetylene hydrogenation is a strongly exothermic process, easy to cause coking and metal agglomeration, and thus leads to deactivation. In this work, Pd/TiO 2 with different oxygen vacancies (V o ) were synthesized by controlling reduction temperature in 300–700°C, in which Pd/TiO 2 -HT300 (HT is reduction temperature) possessed the highest V o content. It was found highly dispersed Pd nanoparticles adjacent to more V o exhibited enhanced catalytic behavior (near 100% conversion at 55°C with 80% selectivity and turnover frequency of 0.12 s −1 ) due to hydrogen spillover generation and electron donation originating from V o sites, confirmed by in situ x-ray photoelectron spectroscopy, in situ Raman, and H 2 -temperature programmed desorption. More importantly, the increasing V o sites trap the released heat and devote to a decrease of heat accumulation over a single active Pd site, and consequently inhibit Pd agglomeration and polymerization, affirmed by high-resolution transmission electron microscopy, CO chemisorption, and thermogravimetric analysis.
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JOURNAL OF NANOBIOTECHNOLOGY
·
2023
·Vol. 21
·期 1
·1-15
·
IF 10.2
Su Runping,Gu Jingjing,Sun Juanjuan,Zang Jie,Zhao Yuge,Zhang Tingting,Chen Yingna,Chong Gaowei,Yin Weimin,Zheng Xiao,Liu Bingbing,Huang Li,Ruan Shuangrong,Dong Haiqing,Li Yan,Li Yongyong
Antigen self-assembly nanovaccines advance the minimalist design of therapeutic cancer vaccines, but the issue of inefficient cross-presentation has not yet been fully addressed. Herein, we report a unique approach by combining the concepts of “antigen multi-copy display” and “calcium carbonate (CaCO 3 ) biomineralization” to increase cross-presentation. Based on this strategy, we successfully construct sub-100 nm biomineralized antigen nanosponges (BANSs) with high CaCO 3 loading (38.13 wt%) and antigen density (61.87%). BANSs can be effectively uptaken by immature antigen-presenting cells (APCs) in the lymph node upon subcutaneous injection. Achieving efficient spatiotemporal coordination of antigen cross-presentation and immune effects, BANSs induce the production of CD4 + T helper cells and cytotoxic T lymphocytes, resulting in effective tumor growth inhibition. BANSs combined with anti-PD-1 antibodies synergistically enhance anti-tumor immunity and reverse the tumor immunosuppressive microenvironment. Overall, this CaCO 3 powder-mediated biomineralization of antigen nanosponges offer a robust and safe strategy for cancer immunotherapy.
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RARE METALS
·
2023
·Vol. 42
·期 5
·1516-1525
·
IF 8.8
Wang Mei-Ling,Zhao Jin,Wang Jin-Jin,Zhang Jun-Ming,Tian Yu-Zhu,Yue Zhi-Zhu,Li Dong,Hu Tian-Jun,Jia Jian-Feng,Wu Hai-Shun
metal oxide electronic interactions in composite electrocatalysts have a considerable impact on their catalytic capability. In this study, we successfully synthesized an electrocatalytic material composed of MoO 3 /C species-supported Pd nanoparticles (Pd-MoO 3 /C) using a convenient hydrothermal method, which exhibited excellent catalytic activities for both ethanol oxidation and oxygen reduction in KOH media. The specific activity of Pd-MoO 3 /C toward ethanol oxidation with MoO 3 loading (40 wt%) was ~ 2.6 times greater than that for the commercial Pd/C (10 wt%) with the same Pd content. In particular, the activity could effectively hold up to ~ 60% of its maximum activity after 500-cycle tests, demonstrating improved cyclical stability. Notably, the fast electron transfer kinetics toward oxygen reduction for Pd-MoO 3 /C (40%) were also comparable to those of commercial Pt/C (20 wt%) catalysts. These superior electrochemical features are primarily derived from the stronger electronic coupling between Pd and MoO 3 through charge transfer, which can supply more active centers and improve the anti-poisoning ability. Meanwhile, the MoO 3 species in the Pd-MoO 3 /C composite may provide additional benefits in terms of electrical conductivity and dispersion. Graphical Abstract
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APPLIED CATALYSIS A-GENERAL
·
2022
·
IF 5.723
Yi-Tian Wang,Si-Ming Wu,Guo-Qiang Luo,Ge Tian,Bo-Jun Zeng,Li-Ying Wang,Shi-Tian Xiao,Jing-Xian Wu,Ao Wu,Kang-Jun Wu,Silvia Lenaerts,Xiao-Yu Yang
Dual active sites from acidic zeolite and Pd are not only capable of catalyzing multiple type of reactions, but could also generate unique functions owing to the synergy between metals and acidic sites. However, there are only a few reports on the investigation of the synergy of acid/Pd dual sites in TS-1. Herein, TS-1 confined Pd catalyst with mesoporous silica shell (Pd@TS-1 @meso-SiO 2 ) has been successfully synthesized and its synergy effect contributes to the enhanced conversion rate (19.2%) and selectivity (74.7%) on styrene oxidation . The interaction between Pd and TS-1 has been investigated by EPR and 1 H NMR techniques, the experimental measurements show an obvious change in the signal distribution of weakly acidic terminal hydroxyls and hydrogen-bonding silanols. The schematic illustration of selective styrene oxidation in the model of Pd@TS-1 @meso-SiO 2 is proposed to clarify the synergistic effect on styrene oxidation between TS-1 and Pd nanoparticles at an atomic-/nanoscale.
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Journal of Energy Chemistry
·
2023
·
IF 13.1
Jun Li,Liying Cai,Xiaosi Liang,Shuke Huang,Xiaosha Wang,Yongshuai Kang,Yongjian Zhao,Lei Zhang,Chenyang Zhao
Light-metalloid-atom-doped Pd interstitial nanoalloy is promising candidate for electrocatalysis because of the favorable electronic effect. Herein, an innovative method was developed to synthesize C-doped Pd interstitial nanoalloy using palladium acetate both as metal precursor and C dopant. Elaborate characterizations demonstrated that C atoms were successfully doped into the Pd lattice via self-catalytic decomposition of acetate ions. The as-synthesized C-doped Pd catalysts showed excellent activity and durable stability for formic acid electrooxidation. The mass activity and specific activity at 0.6 V of C-doped Pd were approximately 2.59 A/mg and 3.50 mA cm −2 , i.e., 2.4 and 2.6 times of Pd, respectively. DFT calculations revealed that interstitial doping with C atoms induced differentiation of Pd sites. The strong noncovalent interaction between the Pd sites and the key intermediates endowed Pd with high-selectivity to direct routes and enhanced CO tolerance. This work presents a sites-differentiation strategy for metallic catalysts to improve the electrocatalysis.
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International Journal of Nanomedicine
·
2023
·
IF 8
Yu Hei,Binhong Teng,Ziqian Zeng,Siqi Zhang,Qian Li,Jijia Pan,Zuyuan Luo,Chunyang Xiong,Shicheng Wei
Background Immune checkpoint blockades (ICBs) are a promising treatment for cancers such as melanoma by blocking important inhibitory pathways that enable tumor cells to evade immune attack. Programmed death ligand 1 monoclonal antibodies (aPDL1s) can be used as an ICB to significantly enhance the effectiveness of tumor immunotherapy by blocking the PD-1/PD-L1 inhibitory pathway. However, the effectiveness of aPDL1s may be limited by low selectivity in vivo and immunosuppressed tumor microenvironment including hypoxia.Purpose To overcome the limitations, we develop a multifunctional immunoliposome, called CAT@aPDL1-SSL, with catalase (CAT) encapsulated inside to overcome tumor hypoxia and aPDL1s modified on the surface to enhance immunotherapeutic effects against melanoma.Methods The multifunctional immunoliposomes (CAT@aPDL1-SSLs) are prepared using the film dispersion/post-insertion method. The efficacy of CAT@aPDL1-SSLs is verified by multiple experiments in vivo and in vitro.Results The results of this study suggest that the multifunctional immunoliposomes preserve and protect the enzyme activity of CAT and ameliorate tumor hypoxia. Moreover, the enhanced cellular uptake of CAT@aPDL1-SSLs in vitro and their in vivo biodistribution suggest that CAT@aPDL1-SSLs have great targeting ability,resulting in improved delivery and accumulation of immunoliposomes in tumor tissue.Finally, by activating and increasing the infiltration of CD8+ T cells at the tumor site, CAT@aPDL1-SSLs inhibit the growth of tumor and prolong survival time of mice,with low systemic toxicity.Conclusion In conclusion, the multifunctional immunoliposomes developed and proposed in this study are a promising candidate for melanoma immunotherapy, and could potentially be combined with other cancer therapies like radiotherapy and chemotherapy to produce positive outcomes.
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JOURNAL OF CATALYSIS
·
2023
·
IF 7.3
Xiao-Chao Chen,Tian Lan,Jian Zhu,Sibin Ying,Guang-Hui Shi,Kai-Chun Zhao,Lin Guo,Yong Lu,Ye Liu
The tripodal phosphine [ L1 , 1,1,1-tris(diphenylphosphino-methyl)ethane] was applied to control the activity, regioselectivity, and stability of the involved Pd-catalyst in anti-Markovnikov hydroaminocarbonylation of alkenes with aromatic amines for the synthesis of linear-amides. Due to the unique characters of L1 in terms of the steric bulkiness, the switching-coordination mode from tripodal phosphine to bidental one, and the robustness against moisture and oxygen, L1 conferred to Pd-catalyst with the high activity, good regioselectivity, and excellent stability for this carbonylation, leading to 44 ∼ 87 % yields of the target amides with L/B of greater than 80/20. The in situ high-pressure FT-IR analysis and the DFT calculations verified that L1 not only promoted the formation and stability of Pd II -H active species (ν ca. 1932 cm −1 ) but also facilitated the anti-Markovnikov’s addition of alkenes with Pd II -H bond due to the favorable energy level of linear intermediate ( B-1 ). In addition, since L1 can coordinate to Pd(II)-center as a bidental chelator as fulfill catalysis and then coordinate to Pd(0)-center as an tripodal pincer, Pd-catalyst was protected timely by L1 against metal-deposition (Pd 0 -black precipitation) to guarantee its stability for recycling uses for 5 runs without activity loss.
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JOURNAL OF ALLOYS AND COMPOUNDS
·
2023
·
IF 6.2
Mingna Chu,Kai Cui,Yan Zhou,Xiuzhi Yuan,Wei Qin,Yang Li,Xiaohong Wu
Enhancing the photoreduction of carbon dioxide (CO 2 ) to produce valuable chemicals, such as carbon monoxide (CO), is of significant importance. The bottleneck in developing advanced catalysts lies in the rational design of catalytic centers with efficient CO 2 activation and hydrogen proton production. In this work, palladium nanoparticles (Pd NPs) were successfully modified on UiO-66-NH 2 -Zn SAs (UN-Zn SAs) by a photo-deposition method. The optimized photocatalyst , 4 Pd NPs-UN-0.7Zn SAs, demonstrated exceptional performance in converting CO 2 to CO, exhibiting approximately 1.4-fold and 7.8-fold enhancements compared to UN-0.7Zn SAs and UN, respectively. A combination of time-resolved photoluminescence spectroscopy and electron paramagnetic resonance results unveiled that the introduction of Pd NPs effectively promoted the photogenerated charge separation and facilitated water activation to produce more hydrogen protons. The generated hydrogen protons were subsequently coupled with nearby CO 2 that was activated by Zn SAs, thus achieving the facile water-activation-induced CO 2 reduction process. Theoretical calculations further confirmed that the heterogeneous synergistic effects between Zn SAs and Pd NPs lowered the energy barrier for the rate-limiting step of CO 2 conversion to COOH* , thereby achieving efficient photocatalytic CO 2 reduction reactions. This work provides a new perspective on the development of efficient catalysts for the effective conversion of CO 2 .
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2023
·
IF 7.2
Lei Yue,Linjie Zhao,Jingwei Hou,Junyan Wang,Jiamao Li,Chengjian Xiao
Large amounts of tritiated water (HTO) will be produced during the operation of nuclear power plants and fusion devices, which is harmful to the environment and human due to its radioactivity and toxicity. So, the tritium concentration of tritiated water must be reduced to a very low value before discharge. Hydrogen-water isotope exchange reaction (H 2 + HTO→H 2 O + HT) based on palladium membrane reactor has been proposed to process tritiated water. However, a comprehensive study about the influence of operation parameters on the membrane reactor performance is insufficient, which is not conducive to the design of reactor in practical application. Moreover, the commonly used Pt/Al 2 O 3 or Ni/SiO 2 catalysts are not active for tritiated water dissociation, so the catalytic activity of these catalysts is not high. In order to process tritiated water more effectively, a two-stage membrane reactor has been designed and established in this work, and Pt/TiO 2 catalyst with rich oxygen vacancies is used to catalyze the hydrogen-water isotope exchange reaction for the first time. The membrane reactor performance shows an approximate linear relationship with a new combined parameter S 0.5 P 1.5 R / F 2 ( S is membrane area , F is water flow rate , P is vapor partial pressure, R is swamping ratio), which can be used predict the membrane performance . The isotope exchange reaction activity of Pt/TiO 2 is better than that of Pt/Al 2 O 3 due to its good ability for water dissociation and the hydrogen spillover effect. At last, a tritiated water processing experiment by using two-stage membrane reactor with Pt/TiO 2 catalyst with rich oxygen vacancies has been carried out. The tritium decontamination factor reaches 40588, which is the highest experimental value so far. The results indicate that the two-stage Pd membrane reactor based on hydrogen-water isotope exchange reaction is an efficient technology for tritiated water processing.
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Journal of Physical Chemistry C
·
2022
·
IF 4.177
Jiarui Zhao,Junhong Fu,Jian Wang,Kaixin Tang,Qi Liu,Jiahui Huang
The Pd/TiO2 catalysts with varying Pd nanoparticle sizes are used to study the control of selectivity toward the hydrogenation of 3-nitrostyrene (3-NS). Our results show the selectivities of 3-vinylanilline (3-VA) rise by decreasing the particle size, while the selectivity of 3-ethylnitrobenzene (3-EN) is the opposite. However, over the Pd/SiO2 catalysts, 3-EN moieties are the dominant product regardless of their differences in particle size. We find that the electronic interactions between Pd NPs and the TiO2 support rise by decreasing particle size, as a result, creating more admetals on the Pd NPs in contact with TiO2, which favorably adsorb the nitro group of 3-NS, thus resulting in enhanced selectivity of 3-VA. However, the classical strong metal–support interactions (SMSI) induced by reduction at elevated temperatures play no significant role in the controlling of selectivities of 3-VA and 3-EN. The SiO2-supported Pd NPs without electronic metal–support interactions (EMSIs) prefer the reduction of the vinyl group of 3-NS. This work underlines the importance of EMSI governing the selectivity for hydrogenation of unsaturated nitroarene reactions.
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ENERGY
·
2022
·
IF 8.857
Heping Xie,Hailong Liao,Shuo Zhai,Tao Liu,Yifan Wu,Fuhuan Wang,Junbiao Li,Yuan Zhang,Bin Chen
Using aqueous Zn–CO 2 batteries to store renewable energy and produce valuable chemicals using CO 2 as the source is a promising method for CO 2 mitigation, that is alternative to traditional energy-costing CO 2 capture/storage technologies. However, the lack of efficient CO 2 -reduction catalysts significantly hinders the efficiency of such batteries. In this study, an efficient perovskite cathode, Pd-doped La 2 CuO 4 , was successfully developed for the cathodic CO 2 reduction reaction (CO 2 RR), and the optimal doping ratio of La 2 Cu 1-x Pd x O 4 ( x = 0.05) was determined. Compared with the pristine La 2 CuO 4 catalyst, the current density for the CO 2 RR in the H-cell and the Faraday efficiency of CO production are both increased by ∼50% when operated −1.0 V (vs RHE). As a result, the peak power density of a Zn–CO 2 battery using the Pd-doped La 2 CuO 4 catalyst reached 0.75 mW cm −2 at 2.23 mA cm −2 by an enhancement ratio of 25%. Density functional theory calculations revealed that the *CO desorption processes on the cathode were enhanced owing to Pd doping, which accounted for the enhanced CO 2 RR activity and selectivity. The findings of this study show the potential application of perovskite catalysts in the cathode of Zn–CO 2 batteries and provide an effective method for battery performance enhancement via the facile Pd doping.
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CHEMOSPHERE
·
2022
·
IF 8.943
Jinghao Wang,Huimin Liu,Song Song,Yuancai Chen,Yongyou Hu
Microbial electron output capacity is critical for organic contaminants biodegradation. Herein, original C. freundii JH could oxidate formate in anaerobic respiration, but lack the ability to degrade sulfamethoxazole (SMX). While the incorporation of Pd(0) could effectively improve the electron output via improving the combination between flavins and c-type cytochromes (c-Cyts), increasing the activities of key enzymes (formate dehydrogenase , hydrogenase, F 0 F 1 -ATPases), etc. More importantly, the presence of Pd(0) caused the NADH dehydrogenase (complex I) nearly in idle, and triggered the decrease of NADH/NAD + ratio and increase of H + -efflux transmembrane gradient, eventually resulting in the electrons diverting from CoQ-involved long respiratory chain (decreasing from 91.67% to 36.25%) to FDH/Hases-based hydrogen-producing short chain (increasing from 22.44% to 84.88%), which further intensified the electron output. Above changes effectively launched and guaranteed the high-level SMX degradation by palladized C. freundii JH, alleviating the ecotoxicity of SMX in aquatic and terrestrial environments. These conclusions provided the new view to regulate the microbial electron output behaviors.
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