A Mechanistic Study of Methanol Steam Reforming on Ni2P Catalyst

Almithn, Abdulrahman; Alhulaybi, Zaid

doi:10.3390/catal12101174

Cited by 13 publications

(8 citation statements)

References 63 publications

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“…Next, we present a thorough analysis of the reaction pathways shown in Scheme 1 on Ni and Ni 12 P 5 . We compare these results with our prior work on Ni 2 P to elucidate the effects of the P:Ni atomic ratio on selectivity and reactivity [ 32 ]. The reaction network, as illustrated in Scheme 1 , serves as the basis for our investigation.…”

Section: Resultsmentioning

confidence: 97%

“…The primary goal of catalyst performance enhancement for MSR is to increase the rate of hydrogen production and improve CO 2 selectivity while using a thermally stable material. Transition metal phosphides (TMPs) have emerged recently as a highly versatile class of catalysts which can be used for a wide range of applications due to their unique selectivity and resistance to coke formation [ 29 , 30 , 31 , 32 , 33 ]. Among those TMPs, nickel phosphides (Ni x P y ) have been previously examined for C–O bond cleavage in biomass-derived molecules [ 34 , 35 ].…”

Section: Introductionmentioning

confidence: 99%

“…In our previous study, we explored the reaction network shown in Scheme 1 over the Ni 2 P(001) surface using density functional theory (DFT) calculations [ 32 ]. Our DFT-derived activation barriers indicate that methanol decomposition on the Ni 2 P(001) surface occurs through CH 3 OH* → CH 3 O* → CH 2 O* → CHO* → CO*.…”

Section: Introductionmentioning

confidence: 99%

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Effects of P:Ni Ratio on Methanol Steam Reforming on Nickel Phosphide Catalysts

Almithn

2023

Molecules

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This study investigates the influence of the phosphorus-to-nickel (P:Ni) ratio on methanol steam reforming (MSR) over nickel phosphide catalysts using density functional theory (DFT) calculations. The catalytic behavior of Ni(111) and Ni12P5(001) surfaces was explored and contrasted to our previous results from research on Ni2P(001). The DFT-predicted barriers reveal that Ni(111) predominantly favors the methanol decomposition route, where methanol is converted into carbon monoxide through a stepwise pathway involving CH3OH* → CH3O* → CH2O* → CHO* → CO*. On the other hand, Ni12P5 with a P:Ni atomic ratio of 0.42 (5:12) exhibits a substantial increase in selectivity towards methanol steam reforming (MSR) relative to methanol decomposition. In this pathway, formaldehyde is transformed into CO2 through a sequence of reactions involving CH2O*→ H2COOH* → HCOOH* → HCOO* → CO2. The introduction of phosphorus into the catalyst alters the surface morphology and electronic structure, favoring the MSR pathway. However, with a further increase in the P:Ni atomic ratio to 0.5 (1:2) on Ni2P catalysts, the selectivity towards MSR decreases, resulting in a more balanced competition between methanol decomposition and MSR. These results highlight the significance of tuning the P:Ni atomic ratio in designing efficient catalysts for the selective production of CO2 through the MSR route, offering valuable insights into optimizing nickel phosphide catalysts for desired chemical transformations.

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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Effects of P:Ni Ratio on Methanol Steam Reforming on Nickel Phosphide Catalysts

Almithn

2023

Molecules

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“…For example, nickel phosphide catalysts exhibit enhanced selectivity towards breaking tertiary 3 C-O bonds in oxygenate compounds, in contrast to pure nickel catalysts where secondary 2 C-O bond cleavage is favored [24]. Furthermore, phosphorus incorporation improved activity and selectivity in other reactions, such as methanol steam reforming and methane activation [25,26]. These findings suggest that phosphorus modification could potentially fine-tune catalytic properties for specific target reactions [27].…”

Section: Introductionmentioning

confidence: 99%

Phosphorus Modification of Iron: Mechanistic Insights into Ammonia Synthesis on Fe2P Catalyst

Almithn

2024

Molecules

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Ammonia (NH3) is a critical chemical for fertilizer production and a potential future energy carrier within a sustainable hydrogen economy. The industrial Haber–Bosch process, though effective, operates under harsh conditions due to the high thermodynamic stability of the nitrogen molecule (N2). This motivates the search for alternative catalysts that facilitate ammonia synthesis at milder temperatures and pressures. Theoretical and experimental studies suggest that circumventing the trade-off between N–N activation and subsequent NHx hydrogenation, governed by the Brønsted–Evans–Polanyi (BEP) relationship, is key to achieving this goal. Recent studies indicate metal phosphides as promising catalyst materials. In this work, a comprehensive density functional theory (DFT) study comparing the mechanisms and potential reaction pathways for ammonia synthesis on Fe(110) and Fe2P(001) is presented. The results reveal substantial differences in the adsorption strengths of NHx intermediates, with Fe2P(001) exhibiting weaker binding compared to Fe(110). For N–N bond cleavage, multiple competing pathways become viable on Fe2P(001), including routes involving the pre-hydrogenation of adsorbed N2 (e.g., through *NNH*). Analysis of DFT-derived turnover rates as a function of hydrogen pressure (H2) highlights the increased importance of these hydrogenated intermediates on Fe2P(001) compared to Fe(110) where direct N2 dissociation dominates. These findings suggest that phosphorus incorporation modifies the ammonia synthesis mechanism, offering alternative pathways that may circumvent the limitations of traditional transition metal catalysts. This work provides theoretical insights for the rational design of Fe-based catalysts and motivates further exploration of phosphide-based materials for sustainable ammonia production.

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“…Here, we explore the catalytic performance of the Ni 2 P catalyst doped with Fe and Ru for ammonia synthesis using DFT. We have previously shown that incorporating phosphorus atoms in nickel phosphide catalysts can alter the catalytic behavior of Ni atoms, leading to improved selectivity for various catalytic reactions [19][20][21]. The P atoms introduce weak binding surface sites that disrupt the metal ensembles.…”

Section: Introductionmentioning

confidence: 99%