Pyrolysis Temperature Tunes the Catalytic Properties of CuBTC-Derived Carbon-Embedded Copper Catalysts for Partial Hydrogenation

Abstract

A family of carbon-embedded copper catalysts was synthesized by pyrolyzing copper benzene-1,3,5-tricarboxylate (Cu-BTC) at various temperatures ranging from 400 to 900 °C. Characterization of catalysts demonstrated that the density of defect sites on the carbon support increases with an increase in the pyrolysis temperature leading to an increase in the electron density on the copper sites. Catalytic performance tests on 1,3-butadiene hydrogenation showed that the performance becomes more stable as the pyrolysis temperature increases above 800 °C such that the catalyst prepared by pyrolysis at 900 °C provided a stable performance for more than 12 h, while the one prepared at 400 °C was deactivating by >25%. Data further demonstrated a strong dependence of the turnover frequencies to the defect site density on the carbonaceous layer. These results present a versatile approach for preparing carbon-embedded copper catalysts with tunable electronic structure and consequent catalytic properties.

InNi3C0.5@C-derived InNi3 alloy as a coke-resistant low-temperature catalyst for selective butadiene hydrogenation

“…On the other hand, replacing precious metal catalysts with cheap candidates is attractive in heterogeneous catalysis. For BD hydrogenation, distinct catalytic systems based on cheap transition metals have been reported in the last decade, including Cu, [15][16][17][18] Ni, [19][20][21] Fe, 22 Co, 23,24 and Mo. 25,26 Nonetheless, catalyst deactivation owing to the deposition of carbonaceous materials is frequently reported in the literature (Cu, 17,18 Ni, 20 Fe, 22 Co, 23,24 Mo (ref.…”

Carbonaceous deposits on cobalt particles reverse the catalytic patterns in butadiene hydrogenation

“…However, considering the high price and the increasingly-scarce resources of precious metals, it is highly desirable to explore other catalytic systems based on cheap and abundant metals. A literature survey shows that Cu is regarded as one of the promising candidates to replace precious metals, [15][16][17][18][19] and thus has received much attention. On the other hand, there are only scarce reports on other cheap transition metals, such as Ni, [20][21][22] Fe, 23 Co, 24 and Mo.…”

“…25,26 Among all the screened hydrogenation systems, catalyst deactivation for both precious (Pd, 27,28 Pt, Au, 11,29,30 Ir (ref. 31)) and non-precious metals (Cu, 16,17 Fe, 23 Mo (ref. 25 and 26)) is frequently reported in the literature.…”

“…For instance, a dramatic increase of the total selectivity to butenes ( S butenes ) during catalyst deactivation has been found on Pd, 28 Mo, 25 and Ir (ref. 31) systems, while only modest changes in product distribution are observed on Au, 3 Cu, 17 and Fe (ref. 23) catalysts.…”

“…While an increase in S butenes was reported in deactivated Pd, 28 Mo 2 C, 25 and Ir (ref. 31) systems, the influence was more modest on Au, 3 Cu, 17 and Fe (ref. 23) catalysts.…”