Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain

Yang, Yang; Zhu, Xiaojuan; Wang, Lili; Lang, Junyu; Yao, Guidong; Qin, Tian; Ren, Zhouhong; Chen, Liwei; Liu, Xi; Li, Wei; Wan, Ying

doi:10.1038/s41467-022-30540-z

Cited by 56 publications

(53 citation statements)

References 61 publications

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“…15). This demonstrated that Pd in Pd/Nb 2 C possess more populated 3d state electrons 30,49 , which is in accordance with the XPS results (Supplementary Fig. 16).…”

Section: Resultssupporting

confidence: 89%

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Zhao

Qiu

Huang

et al. 2022

Preprint

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2D metallene nanomaterials have spurred considerable attention in heterogeneous catalysis by virtue of sufficient unsaturated metal atoms, high specific surface area and surface strain. Nevertheless, the strong metallic bonding in nanoparticles aggravates the difficulty in the controllable regulation of the geometry of metallenes. Here we propose an efficient galvanic replacement strategy to construct Pd metallenes loaded on Nb2C MXenes at room temperature, which is triggered by ultra-strong metal-support interaction based on MD simulation. A combination of electron microscopy, synchrotron X-ray absorption spectroscopy characterizations and theoretical calculations confirm that the Pd metallenes feature a chair structure of six-membered ring with the coordination number of Pd as low as 3. The tripodal Pd metallenes promote the diffusion of alkenes as the effective Pd atoms directly bonded with alkenes decreased compared with traditional Pd (111). As a consequence, the Pd/Nb2C delivers an outstanding turnover frequency of 10372 h− 1 and a high selectivity of 96% at 25 oC in the semihydrogenation of alkynes without compromising the stability. This strategy is general and scalable considering the plentiful members of the MXene family, which can set a foundation for the design of novel supported-metallene catalysts for demanding transformations.

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“…15). This demonstrated that Pd in Pd/Nb 2 C possess more populated 3d state electrons 30,49 , which is in accordance with the XPS results (Supplementary Fig. 16).…”

Section: Resultssupporting

confidence: 89%

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Zhao

Qiu

Huang

et al. 2022

Preprint

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“…As listed in Table S3, the E D values of the H, N, and S atoms are 36.4, 86.5, and 129.9 kJ mol –1 , respectively. Thus, although the H, N, and S atoms are strongly adsorbed at the Pd(111) surface site, they can also exist at the Pd(111) subsurface site, which is also confirmed by the previously reported findings; for example, H can exist at the Pd subsurface as the Pd-hydride. , A recent study reported the successful synthesis of Pd nanocatalysts with interstitial N and S atoms …”

Section: Resultssupporting

confidence: 84%

“…The differential charge density also proves that only B or P heteroatoms lose an electron to the metal Pd, which is consistent with the electronegativity order of N (3.04) > S (2.58) > C (2.55) > H (2.20) > P (2.19) > B (2.04). Compared to the Pd catalyst, as the coverage of the same heteroatom increases, more charges are transferred between the heteroatom and surface Pd atoms, which plays a key role in regulating catalytic performance; , for example, as the d -charge of subsurface heteroatom-doped Pd increases, the adsorption configuration of CC functional groups changes and the adsorption ability on the catalyst becomes weaker, which was beneficial to the improvement of olefin selectivity, and the TOF value of 2-methyl-3-butyn-2-ol (MBY) hydrogenation increases linearly . Further, previous studies showed that the d-band center far from the Fermi level could improve CH x hydrogenation activity over metal catalysts .…”

Section: Resultsmentioning

confidence: 99%

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Enhancing Catalytic Performance through Subsurface Chemistry: The Case of C₂H₂ Semihydrogenation over Pd Catalysts

Zhao

Wang

et al. 2022

ACS Appl. Mater. Interfaces

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Subsurface chemistry in heterogeneous catalysis plays an important role in tuning catalytic performance. Aiming to unravel the role of subsurface heteroatoms, C 2 H 2 semihydrogenation on a series of Pd catalysts doped with subsurface heteroatom H, B, C, N, P, or S was fully investigated by density functional theory (DFT) calculations together with microkinetic modeling. The obtained results showed that catalytic performance toward C 2 H 2 semihydrogenation was affected significantly by the type and coverage of subsurface heteroatoms. The Pd-B 0.5 and Pd-C 0.5 catalysts with 1/2 monolayer (ML) heteroatom coverage, as well as Pd-N, Pd-P, and Pd-S catalysts with 1/16 ML heteroatom coverage, were screened to not only obviously improve C 2 H 4 selectivity and activity but also effectively suppress green oil. The essential reason for subsurface heteroatoms in tuning catalytic performance is attributed to the distinctive surface Pd electronic and geometric structures caused by subsurface heteroatoms. In the Pd-B 0.5 and Pd-C 0.5 catalysts, the Pd surface electronic and geometric effects play the dominant role, while the geometric effect plays a key role in the Pd-N, Pd-P, and Pd-S catalysts. The findings provide theoretically valuable information for designing high-performance metal catalysts in alkyne semihydrogenation through subsurface chemistry.

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“…When the transition metal is modified by the heteroatom, the electronic structure of the metal surface will change, especially the d charge, and then, the adsorption configuration and adsorption energy of key species will be greatly changed. − For example, Yang et al experimentally and theoretically explored the relationship between the d-band electron structure of Pd and the catalytic performance of alkynol semihydrogenation by introducing different types of heteroatoms, including B, P, C, S, and N, into the subsurface of Pd(111) and found that with the number of electrons occupying the d -level increasing, the bond strength between the CC bond and Pd is enhanced and the TOF value of 2-methyl-3-butyn-2-ol (MBY) hydrogenation increases linearly. On the contrary, the adsorption energy of 2-methyl-3-buten-2-ol (MBE) is weakened with the increase in the d charge, and the adsorption configuration is changed from the di-σ adsorption model of the CC bond to the vertical adsorption model of the O–H bond, which is conducive to the desorption of MBE, and the TOF value of MBE hydrogenation is significantly reduced, so the selectivity of MBE is greatly improved.…”

Section: Resultsmentioning

confidence: 99%

Cu Catalysts Doped with a Heteroatom into the Subsurface: Unraveling the Role of Subsurface Chemistry in Tuning the Catalytic Performance of C₂H₂ Selective Hydrogenation

Wang

Guo

et al. 2022

ACS Appl. Mater. Interfaces

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Heteroatoms doped into the subsurface of transition metals play a vital role in heterogeneous catalysis via either expressing surface structures or even directly participating in the reaction. Herein, DFT calculations and microkinetic modeling are implemented to examine C2H2 selective hydrogenation over heteroatom (H, B, C, N, or P)-doped Cu(111) and Cu(211) subsurfaces, which are compared with pure Cu(111) and Cu(211) to unravel the role of subsurface chemistry in tuning the surface structure and further regulating catalytic performance. Our results indicate that the catalytic performance toward C2H2 selective hydrogenation is closely related to the type of doped subsurface heteroatom and the Cu surface coordination environment, which can be attributed to the simultaneous change of Cu surface geometric and electronic structures. Catalytic performance improvement over the heteroatom-doped Cu(111) is generally better than that over the doped Cu(211); especially, B- or N-doped Cu(111) has excellent C2H4 activity and selectivity and greatly inhibits green oil. For the heteroatom-doped Cu(211), better performance is only obtained on P-Cu(211), which is still lower than the B- and N-doped Cu(111). The subsurface heteroatom doping should focus on high-coordination Cu(111) instead of low-coordination Cu(211). AIMD simulations verified the thermal stability of B-Cu(111) and N-Cu(111); both were screened out to be the most suitable catalysts toward C2H2 hydrogenation. This work clearly unravels the role of subsurface chemistry in heterogeneous catalysis and contributes to the rational design of high-performance metal catalysts by tuning surface structures with the heteroatom into the subsurface.

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Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain

Cited by 56 publications

References 61 publications

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Enhancing Catalytic Performance through Subsurface Chemistry: The Case of C₂H₂ Semihydrogenation over Pd Catalysts

Cu Catalysts Doped with a Heteroatom into the Subsurface: Unraveling the Role of Subsurface Chemistry in Tuning the Catalytic Performance of C₂H₂ Selective Hydrogenation

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Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain

Cited by 56 publications

References 61 publications

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation

Enhancing Catalytic Performance through Subsurface Chemistry: The Case of C2H2 Semihydrogenation over Pd Catalysts

Cu Catalysts Doped with a Heteroatom into the Subsurface: Unraveling the Role of Subsurface Chemistry in Tuning the Catalytic Performance of C2H2 Selective Hydrogenation

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Product

Resources

About

Enhancing Catalytic Performance through Subsurface Chemistry: The Case of C₂H₂ Semihydrogenation over Pd Catalysts

Cu Catalysts Doped with a Heteroatom into the Subsurface: Unraveling the Role of Subsurface Chemistry in Tuning the Catalytic Performance of C₂H₂ Selective Hydrogenation