Wednesday, September 28, 2022
HomeChemistryMechanism pushed design of trimer Ni1Sb2 website delivering superior hydrogenation selectivity to...

Mechanism pushed design of trimer Ni1Sb2 website delivering superior hydrogenation selectivity to ethylene

Facebook
Twitter
Pinterest
WhatsApp

Theoretical design of trimer Ni1Sb2 website

We resort to DFT calculations for exploring the visitor Sb bonding with the remoted Ni website, having a spatially and energetically advantageous association, to interrupt the activity-selectivity trade-off. The introduction of antimony remarkably modifications the crystal construction, as revealed by the Wulff development crystals in Supplementary Fig. 1 and Supplementary Tables 1, 2. The Ni(111) and NiSb(101) surfaces, schematically proven in Supplementary Fig. 2, are indicated as essentially the most uncovered surfaces for Ni and NiSb, respectively. Contemplating that essentially the most uncovered floor performs a significant function in acetylene hydrogenation, the Ni(111) and NiSb(101) surfaces had been thus chosen for DFT calculations. The P63/mmc NiSb intermetallic part, exposing the atomically distributed and ensemble Ni1Sb2 websites, and the referenced Ni face-center cubic part had been modeled (Supplementary Fig. 2), that are rationalized by the nice accordance of XRD simulations with the earlier experiments18,19,20,21. On the standard and thermodynamically steady NiSb(101) floor (Supplementary Tables 5, 6), the C2H2 reactant is discovered to thermodynamically bind with the trimer Ni1Sb2 website through a σ-adsorption mode with the adsorption-free vitality of −0.66 eV, whereas the C2H4 product with the one Ni website through a π-adsorption one with that of −0.29 eV. In distinction, on the Ni(111) floor, each the C2H2 and C2H4 want to σ-adsorption modes strongly binding with four- and three-hollow Ni websites (i.e., −2.51 and −0.93 eV), respectively.

The essential function of the visitor Sb was additional elucidated by digital buildings evaluation in contrast with beforehand reported Ga for isolating Ni websites in NiGa intermetallics16 (Fig. 1a and Supplementary Fig. 3). Bader cost analyses reveal much less electron switch related to the adsorption of C2H4 however unexpectedly extra with that of C2H2 on the trimer website as in comparison with the evaluation for these on the Ni floor (Fig. 1b, c). In a different way, the electron switch from the NiGa floor to the adsorbed acetylene molecule is decrease than that from the Ni floor (0.16 e vs 0.58 e), which is in in line with the decrease adsorption vitality on the NiGa floor. These may very well be brought on by the digital interplay between C atoms of acetylene and Sb atoms of trimer Ni1Sb2 website within the σ-adsorption configuration, as advised by the hybridization of C 2p with Sb 5p orbitals (Supplementary Fig. 3). The C 2p orbital DOS profiles of acetylene are related on the NiGa and Ni surfaces, and the C 2p orbital is especially hybridized with the Ni 3d orbital with the absence of clearly hybridized to the Ga 4p orbital. These outcomes verify that the Sb with larger electronegativity than that of Ni is extra promising to be employed to isolate the Ni websites towards enhanced acetylene semi-hydrogenation.

The hydrogenation technique of acetylene through the Horiuti–Polanyi mechanism22,23,24 on the trimer website was subsequently studied by theoretical calculations. On the trimer Ni1Sb2 website, the adsorbed C2H2* is sequentially hydrogenated to C2H3* and C2H4* with free vitality limitations of 1.00 and 1.25 eV (Fig. 1d and Supplementary Fig. 5), respectively. Notably, the hydrogenation of the shaped C2H4* wants to beat a free vitality barrier of 1.05 eV on the trimer Ni1Sb2 website, which is larger than the desorption free vitality of C2H4*. In distinction, the hydrogenation of C2H4* shaped from two-step hydrogenations of C2H2* with free vitality limitations of 1.10 and 0.64 eV is extra facile than the desorption course of on the referenced Ni websites, as advised by the 0.42 eV of hydrogenation free vitality barrier in opposition to the 0.93 eV of the desorption free vitality (Fig. 1d and Supplementary Fig. 4). The competitiveness between the hydrogenation of C2H4* to C2H5* and the desorption of C2H4* determines the ethylene selectivity16,24. These energetic eventualities strongly point out that the hydrogenation of C2H4* is suppressed on the trimer website whereas favorable on the referenced Ni website, that are additional traced to be the unfavorable configuration of the preliminary and transition states on the trimer Ni1Sb2 website. The distances between the H* and C atom of π-adsorbed C2H4 measured for the preliminary and transition states on the Ni1Sb2 website are 3.664 and 1.960 Å (Fig. 1d and Supplementary Fig. 5), respectively, that are remarkably longer than these measured for the configurations on the Ni website, evidencing the thermodynamically unstable configuration of C2H4* and H* on the NiSb(101) floor. These outcomes clearly display that the desorption technique of C2H4 on the trimer website with π-adsorption is extra facile than its over-hydrogenation, and thus the formation of focused ethylene could be promoted. Earlier research have properly proven that the average σ-adsorption mode of acetylene is extra favorable for hydrogenation exercise than the π-adsorption one5,6,7,14. Thus, the average σ-adsorption of acetylene and a weak π-adsorption of ethylene on the trimer Ni1Sb2 website would ship the potential for breaking the trade-off between exercise and selectivity for the response.

Moreover, we additionally investigated the hydrogenation of acetylene on the NiSb(102) floor (Supplementary Figs. 6, 7), which is the secondly principally uncovered floor as advised by the Wulff constructions (Supplementary Fig. 1). The adsorption configuration of C2H2 on the NiSb(102) floor is just like that on the NiSb(101) floor, binding to the trimer Ni1Sb2 website through the σ-adsorption mode with an adsorption-free vitality of −0.89 eV (Supplementary Desk 7). The C2H4 prefers to adsorb on the remoted Ni website with adsorption-free vitality of −0.36 eV (Supplementary Desk 8). On the trimer Ni1Sb2 website of the NiSb(102) floor, the calculated free vitality limitations for the two-step hydrogenation of C2H2* to C2H4* are 0.63 and 1.31 eV (Supplementary Figs. 6, 7), respectively. The desorption free vitality of C2H4* on the NiSb(102) floor is 0.36 eV, which is decrease than the free vitality barrier for the additional hydrogenation to C2H5* (1.10 eV), indicating the ethylene product prefers to desorb from the floor moderately than be hydrogenated. Thus, it may be concluded that the trimer Ni1Sb2 website on the NiSb(102) floor additionally reveals good ethylene selectivity, which has similarities to that on the NiSb(101) floor.

As well as, the dissociation and diffusion of hydrogen had been additionally evaluated on the Ni(111), NiSb(101), and NiSb(102) surfaces. The hydrogen molecule prefers to adsorb on the highest website of Ni(111) floor and subsequently dissociate into two H atoms with an vitality barrier of 0.02 eV and an exothermic vitality of −0.98 eV (Supplementary Fig. 10). These outcomes point out that the dissociation of hydrogen is facile on the Ni(111) floor. In distinction, the hydrogen molecule adsorbed on remoted Ni websites of NiSb(101) and NiSb(102) surfaces dissociate with vitality limitations of 0.83 and 0.80 eV with endothermic vitality of 0.10 and 0.07 eV, respectively (Supplementary Figs. 11, 12). These outcomes reveal that the H2 dissociation is much less facile on the NiSb(101) and NiSb(102) surfaces with remoted Ni websites than that on the Ni(111) floor, which might lower the protection of hydrogen on the NiSb(101) and NiSb(102) surfaces for hydrogenation of shaped ethylene to undesirable ethane. Hydrogen diffusions within the presence of C2 species had been additional simulated to judge the benefit of hydrogen diffusion to the close by C2 species for subsequent hydrogenation. As proven in Supplementary Figs. 13–16, the vitality limitations of hydrogen diffusion on the Ni(111) floor are within the vary of 0.15–0.24 eV through the hydrogenation pathways, whereas these on the NiSb(101) and NiSb(102) surfaces are within the vary of 0.59–0.66 eV and 0.65–0.71 eV, respectively. These outcomes recommend that the diffusion of hydrogen atoms on the Ni(111) floor is extra facile than these on the NiSb(101) and NiSb(102) ones, which may very well be brought on by the elongated Ni-Ni distances on the latter ones. Such simply activated and movable hydrogen atoms on Ni(111) floor might favor the hydrogenation of floor C2 species, together with the shaped ethylene on the floor, and thus result in the suppressed formation of ethylene whereas promoted one in every of ethane.

Acetylene hydrogenation was additionally investigated on the minorly uncovered NiSb(100) through which the gap between the closest Ni websites is 2.643 Å, a lot shorter than these in NiSb(101) and NiSb(102) surfaces (Supplementary Fig. 2). The outcomes are summarized in Supplementary Tables 9, 10 and Supplementary Figs. 8,9. The desorption vitality for ethylene (0.91 eV) is larger than the hydrogenation barrier (0.78 eV) on the NiSb(100) floor, suggesting that the hydrogenation of ethylene shaped on the floor is extra facile than ethylene desorption. Thus, the predominantly uncovered floor NiSb(101) and NiSb(102) surfaces that includes trimer Ni1Sb2 websites dominate the semi-hydrogenation to ethylene, whereas the minorly uncovered NiSb(100) floor results in the over-hydrogenation to ethane. These outcomes spotlight the importance of trimer Ni1Sb2 websites for acetylene semi-hydrogenation.

Synthesis and structural characterizations

Adopted by the theoretical insights, the trimer Ni1Sb2 website was subsequently realized within the NiSb intermetallic catalysts synthesized by an in situ trapping technique (Fig. 2). The majority Sb powder was grinded with the Ni/Mg/Al-LDHs precursors ready by a co-precipitation technique to acquire the Sb-containing LDHs, which was additional handled at 900 °C beneath hydrogen. At such a excessive temperature, bulk Sb was melted right into a molten and movable state. Concurrently, the excessive temperature led to the discount of Ni atoms from Ni ions contained within the LDHs and additional ex-solution from the LDH. The sturdy NiSb metallic bond interplay favors the free Ni atoms to bond with the Sb atoms to type NiSb motifs, which thermodynamically assemble to type the nanoparticles featured with a steady NiSb intermetallic construction. The crystal construction of the synthesized NiSb catalyst was recognized by XRD measurements (Fig. 3a). The diffraction peaks at 36.8°, 59.3°, and 65.2° are akin to the (311), (511), and (440) planes of MgAl2O4 (JCPDS No. 21–1152), and the 2 diffraction peaks at 42.9° and 62.3° are assigned to the (200) and (220) planes of MgO (JCPDS No. 45–0946), respectively. Along with these diffraction peaks of the assist, the XRD sample of the NiSb catalyst reveals typical diffraction peaks at 31.5°, 43.9°, and 46.1° assigned to the (101), (102), and (110) planes of hexagonal NiSb intermetallic part (JCPDS No. 41–1439), respectively. These outcomes indicate the profitable formation of the NiSb intermetallic part within the NiSb catalyst through the technique. In distinction, consultant diffraction peaks at 44.3°, 51.7°, and 76.1° ascribed to the (111), (200), and (220) planes of face-centered cubic Ni part (JCPDS No. 65–0380), respectively, are noticed from the XRD sample of the Ni catalyst.

Fig. 2: Synthesis technique for Ni1Sb2 websites.
figure 2

Schematic illustration for the development of the trimer Ni1Sb2 website within the NiSb intermetallic construction through an in situ trapping of molten Sb by Ni technique facilitated by thermal remedy beneath hydrogen from the Ni/Mg/Al-LDHs precursor.

Fig. 3: Microstructure and morphology of NiSb intermetallic catalyst.
figure 3

a XRD patterns of the synthesized Ni and NiSb catalysts. Typical HRTEM photos and corresponding FFT patterns of b Ni and c NiSb catalysts. HAADF-STEM photos of d Ni and e NiSb catalysts in addition to the corresponding EDS line-scanning profiles. HAADF-STEM EDS mapping analyses of f Ni and g NiSb catalysts.

To confirm the trapping roles of Ni species in LDHs, a referred LDHs with out Ni species was synthesized after which grinded mechanically with Sb powder. After thermal remedy at 900 °C beneath hydrogen, the crystal construction of the as-obtained pattern was comparatively characterised by XRD, which exhibits the absence of diffraction peaks akin to Sb phases (Supplementary Fig. 17). Moreover, the decided content material of Sb on this referred catalyst is near zero (Supplementary Desk 11). These outcomes clearly point out that the movable and molten Sb can’t be trapped by the LDHs with out Ni species and eventually vaporized through the thermal remedy25, and thus might detach from the strong pattern. Additional rising the quantity of Sb within the 2-NiSb catalyst, the place 2 denotes the nominal ratio of Sb/Ni, additionally offers rise to the formation of the NiSb intermetallic part by this trapping technique moderately than the NiSb2 intermetallic part (Supplementary Fig. 17 and Figs. 23,  26), in all probability owing to the NiSb metallic bond interplay with a ratio of 1:1 through the trapping course of. The precise atomic ratio of Sb/Ni is decided to be 1.07 (Supplementary Desk 11), near the nominal one of many NiSb intermetallic part, evidencing that the additional Sb may very well be vaporized after which detach from the strong pattern25. The evaporation of Sb within the precursor of the 2-NiSb through the thermal course of was additional confirmed by thermogravimetric evaluation in Supplementary Fig. 18 and Fig. 19.

Excessive-resolution transmission electron microscopy (HRTEM) photos and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) measurements had been additional carried out to determine microstructural options of monometallic Ni and NiSb catalysts. Supplementary Fig. 20 exhibits the standard HAADF-STEM photos of the Ni and NiSb catalysts, the place the nanoparticles are uniformly distributed with related common particle sizes. The everyday HRTEM photos with the corresponding quick Fourier rework (FFT) patterns of Ni and NiSb catalysts display steady lattice fringes with the spacings of 0.204 and 0.283 nm (Fig. 3b, c), that are assigned to the interplanar spacings of the (111) airplane of face-centered cubic Ni and the (101) airplane of the hexagonal NiSb intermetallics, respectively. Moreover, the energy-dispersive X-ray spectroscopy (EDS) line-scanning analyses for single nanoparticle point out that Ni and Sb are homogeneously distributed over the nanoparticles with the atomic ratio of 1:1 (Fig. 3e and Supplementary Fig. 21), as in contrast with these of Ni catalyst (Fig. 3d and Supplementary Fig. 22). Equally, the EDS mapping analyses for the Ni catalyst exhibit the uniform distribution of Ni inside the monometallic nanoparticles with the absence of Sb (Fig. 3f and Supplementary Fig. 24), whereas these of the NiSb catalyst display that Ni and Sb species are homogeneously distributed in bimetallic nanoparticles (Fig. 3g and Supplementary Fig. 25). All these outcomes level to the profitable fabrication of the NiSb intermetallic part.

Aberration-corrected HAADF-STEM (AC-HAADF-STEM) method was employed for visualizing the atomic construction of the NiSb catalyst. Determine 4a exhibits the standard AC-HAADF-STEM picture of the NiSb catalyst, the place distinct lattice fringes are clearly noticed. The built-in pixel depth profile acquired together with the violet arrow in Fig. 4b reveals that the common spacing alongside this route is 0.31 nm assigned to the (101) airplane of intermetallic NiSb. Equally, the common spacing of one other lattice fringe is decided to be 0.37 nm akin to the (100) airplane of the NiSb intermetallic part. Primarily based on the enlarged picture of atomic distribution in Fig. 4c, the corresponding FFT sample is obtained to derivate the zone axis (Fig. 4d). The atomic distribution predicted by the crystal structural fashions together with the decided [010] zone axis is properly in line with that visualized by AC-HAADF-STEM in Fig. 4c. To additional examine the formation of NiSb intermetallic part in NiSb catalyst, one other nanoparticle in a distinct space can also be randomly chosen to characterize by AC-HAADF-STEM (Fig. 4e). Equally, ordering atomic association with distinct lattice fringe is clearly seen in Fig. 4f, and the built-in pixel depth profile exhibits that the common spacing of such lattice fringe is decided to be 0.23 nm assigned to the (110) airplane of NiSb intermetallic part. The obtained FFT sample in accordance with the enlarged picture gives the zone axis (Fig. 4g, h), primarily based on which the expected association from the best NiSb crystal construction agrees properly with the noticed one. Related outcomes are additionally seen with different particles proven in Supplementary Figs. 27,  28. These unequivocally display the ordering atomic distribution of the NiSb intermetallic part within the synthesized NiSb catalyst.

Fig. 4: Atomic buildings of NiSb intermetallic catalyst.
figure 4

a, e Consultant AC-HAADF-STEM photos of NiSb catalyst together with completely different zone axes. b, f Line depth profiles alongside direct indicated by the violet arrows in a and e. c, g Enlarged views of the areas marked by the yellow rectangles in a and e in addition to the corresponding crystal fashions together with [010] and [001] zones, respectively. d, h The FFT patterns of the NiSb catalyst. i Ni 2p and Sb 4d XPS spectra of the NiSb catalyst. j Normalized XANES spectra and ok ok2-weighted Fourier rework (FT) spectra on the Ni Okay-edge of the Ni foil, Ni, and NiSb catalysts. l The EXAFS oscillation capabilities and m WT-EXAFS contours on the Ni Okay-edge of Ni foil, Ni, and NiSb catalysts.

The formation of the NiSb intermetallic construction would ship outstanding digital interplay between the host Ni and the visitor Sb because of the sturdy hybridization. X-ray photoelectron spectroscopy (XPS) evaluation was thus employed to discover the digital buildings of the catalysts. The peaks positioned at binding energies of 852.3 and 855.9 eV within the Ni 2p XPS spectrum of the Ni catalyst are attributed to Ni0 and Ni2+ (Fig. 4i), respectively. The presence of the Ni2+ species may very well be brought on by the re-oxidation of the Ni catalyst through the ex-situ measurements16,26. Notably, the Ni 2p XPS peaks of the NiSb catalyst shift to larger binding energies by 0.4 eV in contrast with these of the Ni catalyst. In the meantime, the deconvoluted Sb 4d XPS spectra exhibit 4 peaks akin to Sb0 and Sb3+ species (Fig. 4i), which shift to decrease binding vitality in comparison with these of the monometallic Sb27. The constructive shift of Ni 2p XPS peaks and concurrently unfavorable shift of Sb 4d XPS peaks point out electron switch from Ni to Sb, in keeping with the upper electronegativity of the visitor Sb (2.05) than that of the host Ni (1.91). The digital properties and native surroundings of the NiSb catalyst had been additional revealed by X-ray absorption spectroscopy measurements. The normalized X-ray absorption near-edge construction (XANES) spectrum on the Ni Okay-edge of the NiSb catalyst shifts to the place of excessive photon vitality with an elevated depth of white line peak in comparison with that of the Ni foil and the Ni catalyst (Fig. 4j), suggesting the decreased electron density of Ni atoms within the NiSb catalyst because of the electron switch from Ni to the neighboring Sb28,29,30,31. The accrued electron density on the visitor Sb is favorable for binding the electron-deficient acetylene reactant however unfavorable for capturing the electron-rich ethylene product, which supplies rise to the average σ-adsorption of acetylene and π-adsorption of ethylene on the trimer Ni1Sb2 website (Fig. 1b, c).

Moreover, the Fourier rework of prolonged X-ray absorption nice construction (EXAFS) on the Ni Okay-edge of the NiSb catalyst reveals decrease depth on the first nearest-neighbor coordination than that of the Ni catalyst (Fig. 4k), suggesting a decreased Ni-Ni coordination within the NiSb catalyst. Extra importantly, a outstanding peak related to the NiSb coordination is noticed at an extended distance, and the height akin to the Ni-Ni coordination is absent within the EXAFS spectrum of the NiSb catalyst, evidencing the remoted Ni websites by Sb within the intermetallic part. That is additional confirmed by the EXAFS oscillation on the Okay area of the NiSb catalyst (Fig. 4l). The shorter intervals and weaker amplitudes than these of the Ni foil and the referenced Ni catalyst point out the longer coordination distance of NiSb and decrease coordination surroundings within the NiSb catalyst32,33,34,35. Wavelet transforms (WT) analyses of the Ni EXAFS oscillations had been additional carried out to realize extra highly effective proof for strengthening the remoted Ni websites by Sb within the NiSb catalyst (Fig. 4m). The WT-EXAFS contour plots of the Ni foil and the Ni catalyst each present a most at round 8.2 Å−1 contributed by the Ni-Ni coordination. In distinction, the WT-EXAFS contour plot of the NiSb catalyst solely reveals a most at round 10.5 Å−1, which is assigned to the contribution of the Ni-Sb coordination. All of the above structural characterizations clearly reveal the formation of NiSb intermetallic construction featured with the trimer Ni1Sb2 website within the synthesized NiSb catalyst.

Catalytic efficiency of acetylene semi-hydrogenation

The synthesized NiSb catalyst was employed for acetylene hydrogenation within the presence of ethylene along with the referred Ni catalyst. The conversion of acetylene over the NiSb catalyst regularly will increase from 20 to 100% with the rising response temperature from 40 to 260 °C, whereas the selectivity to ethylene maintains to be larger than 90% at such temperature vary (Fig. 5a, b). In distinction, the conversion of acetylene over the monometallic Ni catalyst stays at round 100% on the complete temperature vary, whereas that on the monometallic Sb catalyst is near zero (Fig. 5a). As well as, the selectivity to ethylene will increase with the rising temperature on the Ni catalyst, in all probability because of the favored ethylene desorption16 and thus suppressed formation of ethane (Supplementary Fig. 30), however continues to be a lot decrease than that of the NiSb catalyst (Fig. 5b). Furthermore, the Ni catalyst reveals remarkably larger selectivity to C4 elements than the NiSb catalyst (Supplementary Fig. 31), indicating the promoted coupling technique of C2 species on the Ni catalyst, which is a clue that the steadiness of the Ni catalyst could also be inferior. It must be famous that the excessive conversion of acetylene on the Ni catalyst is owing to the facile formation of ethane and C4 elements moderately than the formation of focused ethylene. The comparability for the calculated formation price of the merchandise demonstrates that the NiSb catalyst reveals a remarkably enhanced formation price of ethylene with clearly suppressed ones of ethane and C4 elements than the Ni catalyst (Supplementary Fig. 38). Notably, the conversion of acetylene and the merchandise selectivities over the 2-NiSb catalyst are near these over the NiSb catalyst (Fig. 5a, b and Supplementary Figs. 30, 31), additionally confirming the formation of NiSb intermetallic part within the 2-NiSb catalyst (Fig. 3a and Supplementary Fig. 17).

Fig. 5: Catalytic performances for acetylene hydrogenation.
figure 5

a C2H2 conversion and b C2H4 selectivity as a perform of response temperature; c Comparability for acetylene conversion and merchandise selectivities of the Ni and NiSb catalysts; d Acetylene conversion and e ethylene selectivity with the time on stream over the Ni and NiSb catalysts.

A extra detailed comparability of the catalytic performances of the Ni and NiSb catalysts in Fig. 5c display that the NiSb catalyst reveals a superb ethylene selectivity as much as 93.2% on the full conversion of acetylene, with the ethane selectivity and C4 selectivity low to three.2 and three.6%, respectively. Nevertheless, the monometallic Ni catalyst exhibits considerably low ethylene selectivity (i.e., −75.5%) at 100% of acetylene conversion. This means that a considerable amount of ethylene within the feed fuel was concurrently hydrogenated to ethane, as evidenced by the excessive ethane selectivity of the Ni catalyst (Fig. 5c). As well as, the selectivity to C4 elements of the Ni catalyst is clearly larger than that of the NiSb catalyst. Earlier research confirmed that the formation of C4 elements in acetylene hydrogenation is especially attributed to the C-C coupling of strongly adsorbed floor species corresponding to acetylene and vinyl36,37,38,39. The upper selectivity to C4 elements suggests a extra facile coupling course of on the Ni catalyst. Moreover, the ethylene selectivity on the full conversion of acetylene on the NiSb intermetallic catalyst is clearly larger than that seen with the beforehand reported NiGa intermetallic catalyst featured with remoted Ni websites by neighboring Ga ones16. This comparability might point out the distinctive digital and geometric results of the neighboring Sb websites within the NiSb intermetallics.

Arrhenius plots for acetylene conversion and product formation had been additional carried out to discover the kinetics benefits of the NiSb catalyst (Supplementary Figs. 32–35). The decided obvious activation vitality for acetylene conversion over the Ni (29.7 kJ/mol) is clearly decrease than that on the NiSb catalyst (43.9 kJ/mol), which signifies that the activation of acetylene on the Ni catalyst is extra facile. Nevertheless, such simply activated acetylene is troublesome to be transformed to the focused ethylene product, as revealed by the a lot larger obvious activation vitality for the formation of ethylene on the Ni catalyst (Supplementary Fig. 33). As a substitute, the obvious activation energies for the formations of ethane and C4 elements on the NiSb catalyst are clearly larger than these on the Ni catalyst (Supplementary Figs. 34,  35). These kinetics outcomes display that the formations of ethane and C4 elements are remarkably extra inert on the NiSb catalyst. In distinction, the formation of focused ethylene on the NiSb catalyst is extra kinetically favorable than these of ethane and C4 elements.

Contemplating that the C4 elements are the precursors of inexperienced oil, the steadiness of the Ni catalyst could be inferior to that of the NiSb catalyst, which is addressed by the steadiness checks for the Ni and NiSb catalysts. As anticipated, the conversion of acetylene on the NiSb catalyst retains at round 92.0% with 93.5% of ethylene selectivity (Fig. 5d, e) however negligible formation of ethane and C4 elements via the 48 h stability testing (Supplementary Figs. 39–40), presenting a superb catalytic stability. Against this, the conversion of acetylene on the monometallic Ni catalyst decreases sharply from the preliminary 95.0% to round 64.0% after response for 48 h, whereas the selectivities to ethylene, ethane and C4 elements are unchanged with the time on stream. These outcomes distinctly display the deactivation of the Ni catalyst through the hydrogenation course of, primarily because of the accrued inexperienced oil on the floor.

The thermogravimetric (TG) analyses had been then carried out for the spent Ni and NiSb catalysts to discover the doable deposition of inexperienced oil. The load lack of the spent Ni catalyst with rising the temperature is round 9.4 wt%, suggesting an apparent accumulation of inexperienced oil on the catalyst (Fig. 6a). Furthermore, the DTG curve reveals a pointy peak at ca. 375 °C with a peak shoulder at ca. 250 °C, which might be ascribed to the combustion of heavy and light-weight hydrocarbons16,40,41, respectively. In distinction, the TG profile of the spent NiSb catalyst exhibits a slight weight reduction on the vary of 120–200 °C, primarily ensuing from the vaporization of physiosorbed water. Notably, the peaks akin to the combustions of sunshine and heavy hydrocarbons are hardly noticed for the spent NiSb catalyst, indicating the negligible formation of inexperienced oil on the catalyst. Pyrolysis fuel chromatography-mass spectrometer (GC-MS) experiments had been additional carried out for the used Ni and NiSb catalysts to discover the compositions of shaped inexperienced oil. Determine 6b exhibits the pyrolysis GC-MS profiles of those catalysts and that of a regular pattern made up of assorted chain hydrocarbons. Clearly, the intensities of peaks noticed with the spent Ni catalyst are a lot stronger than these seen with the used NiSb catalyst, indicating that extra inexperienced oil was shaped and accrued on the Ni catalyst than the NiSb catalyst, which is in good accordance with the TG analyses. As well as, the inexperienced oil accrued on the Ni catalyst accommodates extra heavy hydrocarbons than that on the NiSb catalyst, as quantitatively confirmed by the statistical evaluation for the carbon numbers of the chain hydrocarbons contained within the inexperienced oil (Fig. 6c). The averaged carbon variety of the chain hydrocarbons comprised within the inexperienced oil on the used Ni catalyst is 24.1, clearly bigger than that on the used NiSb catalyst. These unambiguously display the suppressed formation of inexperienced oil through the coupling course of over the NiSb catalyst.

Fig. 6: Coke evaluation.
figure 6

a TG-DTG profiles of the spent Ni and NiSb catalysts. b Pyrolysis GC-MS profiles of inexperienced oil deposited on the Ni and NiSb catalysts the place the usual sample is taken from the refs. 41, 47 and c corresponding statistics for carbon numbers of hydrocarbons contained in inexperienced oil. d Adsorption-free vitality of 1,3-butadiene over the Ni(111) and NiSb(101) surfaces. e Prime and entrance views of the cost density distributions of 1,3-butadiene adsorbed on the Ni(111) and NiSb(101) surfaces. The pink and blue isosurfaces characterize the buildup and depletion of the electron density, respectively, through which the isosurface worth are each 0.005 e·Å−3. The pink arrows point out the route of cost switch between the surfaces and the 1,3-butadiene.

The origin of the restrained formation of inexperienced oil on the intermetallic NiSb floor is additional traced by theoretical calculations. 1,3-butadiene because the precursor for the formation of inexperienced oil, which is shaped through the coupling course of, is revealed to adsorb on the Ni(111) floor through binding with six adjoining Ni atoms with an adsorption-free vitality of −1.47 eV (Fig. 6d). In distinction, 1,3-butadiene binds weakly with two elongated Ni websites on the NiSb(101) floor with an adsorption-free vitality of −0.01 eV. The weaker adsorption of 1,3-butadiene on the NiSb floor than that on the Ni floor is additional evidenced by the much less cost switch between the molecule and the floor (Fig. 6e). These outcomes elucidate that the introduction of Sb destabilizes the 1,3-butadiene molecule on the NiSb floor with remoted Ni websites, which is favorable for the desorption of 1,3-butadiene in opposition to its accumulation and polymerization to inexperienced oil. The efficiency checks strengthen the wonderful selectivity of the trimer Ni1Sb2 website for acetylene semi-hydrogenation predicted by the theoretical calculations.

Adsorption behaviors on trimer Ni1Sb2 website

Temperature-programmed desorption measurements had been additional carried out to discover the distinctive adsorption/desorption behaviors of C2H2 and C2H4 on the Ni and NiSb catalysts. As proven in Fig. 7a, the C2H2-TPD profile of the Ni catalyst presents three legible peaks centered at 168, 320, and 457 °C. In keeping with earlier research, the height on the temperature of 168 °C is attributed to the desorption of weakly π-adsorbed C2H2, and the peaks positioned at 320 and 457 °C are corresponded to the desorption of C2H2 species and/or the corresponding C2-fragments shaped on the elevated temperature di-σ-bonded on bridge Ni websites and multi-σ-bonded on hole Ni websites, respectively42,43,44. The C2H2-TPD profile of the NiSb catalyst exhibits two seen desorption peaks positioned at 124 and 286 °C corresponded to π-adsorbed and σ-adsorbed C2H2, respectively, that are decrease than these of the peaks seen with the profile of the Ni catalyst. The height corresponded on the species desorbed from the hole website is hardly noticed within the C2H2-TPD profile of the NiSb catalyst, suggesting the absence of multi-σ-bonded C2H2 on the hole website, agreeing properly with the outcomes from theoretical calculations (Fig. 1b and Supplementary Tables 3–6). The C2H4-TPD profile of the Ni catalyst shows two peaks centered at 179 and 330 °C (Fig. 7b). In keeping with earlier research42,43,44, the desorption peaks on the temperature under 300 °C are assigned to the continual desorption of the weakly π-adsorbed C2H4 with out decomposition, and people positioned on the temperature larger than 300 °C are assigned to the desorption of C2-fragments decomposed from the strongly σ-bonded C2H4. In distinction, the C2H4-TPD profile of the NiSb catalyst solely demonstrates weakly π-adsorbed ethylene on the NiSb catalyst, which can also be in keeping with the theoretical outcomes.

Fig. 7: Adsorption/desorption and hydrogenation behaviors on Ni1Sb2.
figure 7

a C2H2-TPD and b C2H4-TPD profiles of the Ni and NiSb catalysts. In-situ DRIFTS spectra of the hydrogenation of pre-adsorbed acetylene on c Ni and d NiSb catalysts at elevated temperatures. The assignments of the attribute peaks are schematically proven within the insets above the spectra.

The hydrogenation of pre-adsorbed acetylene on the catalysts had been additional traced by in situ diffuse reflectance infrared Fourier rework spectroscopy (DRIFTS) measurements at rising temperature. Determine 7c, d and Supplementary Figs. 41, 42 present the spectra collected through the hydrogenation of pre-adsorbed acetylene over the Ni and NiSb catalysts at a temperature from 20 to 150 °C. The formation of ethylene on the Ni catalyst is evidenced by the attribute peaks of the CH2 scission and the C=C stretching vibration45 at 1607 and 1709 cm−1, respectively. As well as, the peaks at 2933 and 2968 cm−1 corresponded to the -CH2 uneven stretching of long-chain hydrocarbons and -CH3 uneven stretching of alkanes46, respectively, point out the facile coupling and over-hydrogenation processes on the Ni catalyst. These are in good accordance with noticed larger selectivities to ethane and C4 elements in Fig. 5. On the NiSb catalyst, the formation of ethylene can also be confirmed by the 2 characterization peaks of the CH2 scission and the C=C stretching vibration at 1602 and 1703 cm−1. Notably, the attribute peaks assigned to the alkanes and the long-chain hydrocarbons attenuate considerably on the NiSb catalyst and are nearly laborious to be noticed from the spectra. These reveal the inhibited formations of ethane and the inexperienced oil precursor on the NiSb catalyst. Furthermore, the intensities of the peaks corresponded to ethylene on the NiSb catalyst lower with the rising temperature extra remarkably than these seen with the Ni catalyst, implying the weaker adsorption of ethylene on the NiSb catalyst. These outcomes strengthen the wonderful selectivity of the trimer Ni1Sb2 websites within the NiSb catalyst in opposition to the referred Ni catalyst.

In abstract, we have now employed the distinctive electronegative and p-block traits of visitor Sb to manage the host Ni to realize a trimer Ni1Sb2 website in NiSb intermetallic with superior efficiency for acetylene semi-hydrogenation. Our theoretical outcomes point out that the trimer Ni1Sb2 website within the intermetallic P63/mmc NiSb endows a average σ-adsorption mode for acetylene whereas a weak π-adsorption one for ethylene, implying boosted acetylene semi-hydrogenation. As predicted by the theoretical outcomes, the NiSb catalyst featured with the trimer website fabricated by an in situ trapping technique of molten Sb by Ni reveals a superb ethylene selectivity as much as 93.2% with considerably low selectivities to ethane and C4 elements at 100% of acetylene conversion, prevailing over the referred Ni catalyst. These findings exemplify the design and fabrication of atomically uniform lively websites for fine-tuning configurations of key species to manage the selectivity to the focused product.

Facebook
Twitter
Pinterest
WhatsApp
RELATED ARTICLES

LEAVE A REPLY

Please enter your comment!
Please enter your name here

Most Popular

Recent Comments