INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
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2025
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IF 3.9
Bin Zhang,Xiaodong Guo,Xin Feng,Xiaoxia Duan,Guilong Wang,Chao Yang
The debenzylation reaction of hexabenzylhexaazaisowurtzitane (HBIW) and 2,6,8,12-tetraacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexaazaisowurtzitane (TADBIW) to synthesize 2,6,8,12-tetraacetyl-2,4,6,8,10,12-hexaazaisowurtzitane (TAIW) is the major challenge in the production of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (HNIW). This is primarily attributed to the reaction needing a lot of palladium catalysts, which tend to deactivate rapidly during the process. In this work, a series of Pd(OH)2/C catalysts were successfully prepared through a convenient deposition-precipitation method by controlling the flow rate of the PdCl2 solution. Employing the 10% Pd(OH)2/C–F0.5 sample, the debenzylation reaction was successfully completed with a lower usage of Pd and shorter time of reaction. For the HBIW debenzylation reaction, the yield of TADBIW was 87.4% at low temperature (25 °C) when 1‰ Pd/HBIW was used, and the higher yield was 89.8% at high temperature (45 °C) when 3‰ Pd/HBIW was used. The TADBIW/Pd/h values of them were 42.5 and 95.7, respectively. For the TADBIW debenzylation reaction, the complete conversion of the reactant was realized when Pd/TADBIW was 2‰. The value of TAIW/Pd/h was 154.6 when Pd/TADBIW was 4‰, which was higher than the reports. Compared to the reported catalysts, the dosage of Pd used in the debenzylation reactions of HBIW and TADBIW was significantly decreased. Furthermore, the 10% Pd(OH)2/C–F0.5 sample was recycled six times with similar performance, demonstrating excellent stability. Based on the analysis of characterization results, it is effortless to find that the flow rate of the PdCl2 solution plays a key role in controlling the adsorption behavior of palladium species on activated carbon. The lower flow rate is beneficial to obtaining Pd nanoparticles with a smaller size, a higher proportion of Pd2+, and a higher metal distribution. This study may provide a simple way to develop palladium catalysts with high performance for related applications.
研究领域:
化学工程
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催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Qing-Shan Niu,Yi-Ran Du,Xin-Peng Guo,Jing-Wen Sun,Si-Ping Pang,Bao-Hua Xu
The Pd-catalyzed N-debenzylation of hexabenzylhexaazaisowurtzitane (HBIW) to tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) has provided high yields (up to 90.0 %, 12 h) in batch reactors, however, several phase transition stages during the catalytic process disable the development of a continuous flow system. In this work, we designed Pd-WO m bifunctional catalysts (Pd-WO m /MO n ) for such a transformation under three-phase reaction conditions with high efficiency. Remarkably, TADBIW was obtained with a high yield of 82.5 % upon reacting for 6 h at 40 °C on Pd-WO m (5.0)/CeO 2 (Pd: 1.33 mol%). Experimental studies combined with theoretical analysis reveal the HBIW-to-TADBIW conversion is a stepwise hydrogenolysis-acetyldebenzylation process, wherein the initial hydrogenolysis of Ac 2 O turn over the catalysis. Importantly, the presence of highly dispersed WO m domains with proper size not only facilitates hydrogen spillover from Pd site to the adsorpted Ac 2 O but also accelerates the subsequent dissociation of *Ac 2 O(H), enabling reduction of the overall energy barrier for debenzylation.
研究领域:
化学
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催化科学
✓ 已验证
产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2026
·
IF 2.6
Qian Wang,Rubo Fang,Heng Yuan,Xinyi Zhang,Guilong Hu,Qunfeng Zhang
To address the high consumption and cost of noble metal catalysts during the production of hexanitrohexaazaisowurtzitane (HNIW, CL-20), nitrogen-doped titanium dioxide (TN) was synthesized using urea as a nitrogen source. PdO/TN catalysts were then fabricated via a deposition–precipitation route and applied to the continuous hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane (HBIW). Characterization by XRD, TEM, Raman, XPS, and H₂-TPR revealed that nitrogen incorporation effectively promoted the generation of surface oxygen vacancies and strengthened metal–support interactions, thereby enhancing catalyst stability. Moreover, the oxygen vacancy concentration could be tuned by adjusting calcination conditions. The PdO/TN-400-2 catalyst, prepared at 400 °C for 2 h, exhibited the highest catalytic activity, with an oxygen vacancy fraction of 19.64%. Further decreasing the calcination severity increased defect density but did not yield additional performance gains. These findings demonstrate that nitrogen doping can regulate surface defect chemistry and metal–support coupling, offering a viable strategy for the design of efficient catalysts for hexabenzylhexaazaisowurtzitane (HBIW) debenzylation.
✓ 已验证
产品关联
DOI
高影响因子
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