Nano-Intermetallic InNi3C0.5 Compound Discovered as a Superior Catalyst for CO2 Reutilization

Abstract

Summary CO 2 circular economy is urgently calling for the effective large-scale CO 2 reutilization technologies. The reverse water-gas shift (RWGS) reaction is the most techno-economically viable candidate for dealing with massive-volume CO 2 via downstream mature Fischer-Tropsch and methanol syntheses, but the desired groundbreaking catalyst represents a grand challenge. Here, we report the discovery of a nano-intermetallic InNi 3 C 0.5 catalyst, for example, being particularly active, selective, and stable for the RWGS reaction. The InNi 3 C 0.5 (111) surface is dominantly exposed and gifted with dual active sites (3Ni-In and 3Ni-C), which in synergy efficiently dissociate CO 2 into CO* (on 3Ni-C) and O* (on 3Ni-In). O* can facilely react with 3Ni-C-offered H* to form H 2 O. Interestingly, CO* is mainly desorbed at and above 400°C, whereas alternatively hydrogenated to CH 3 OH highly selectively below 300°C. Moreover, this nano-intermetallic can also fully hydrogenate CO-derived dimethyl oxalate to ethylene glycol (commodity chemical) with high selectivity (above 96%) and favorable stability.

Oxygen-deficient metal oxides supported nano-intermetallic InNi 3 C 0.5 toward efficient CO 2 hydrogenation to methanol

“…In addition, as shown in fig. S10C, linearly adsorbed CO with infrared band at 2077 cm −1 ( 23 ) is detected on InNi 3 C 0.5 /SiO 2 at room temperature. This linear adsorption of CO is also observed on the InNi 3 C 0.5 /ZrO 2 catalysts but exhibits a visible red shift from 2077 to 2075 (InNi 3 C 0.5 / a -ZrO 2 ) and further to 2047 and 2046 cm −1 (InNi 3 C 0.5 / t -ZrO 2 and InNi 3 C 0.5 / m -ZrO 2 , respectively) because of an enhanced electron back-donation from InNi 3 C 0.5 to the anti-bonding orbitals of CO ( 38 ).…”

“…The supports desorb little CO 2 , showing the poor ability to adsorb CO 2 , while the unsupported InNi 3 C 0.5 desorbs a huge amount of CO 2 at 510°C (with trace CO) and 637°C (concomitantly with abundant CO; Fig. 3D ), respectively assigned to the nondissociated CO 2 adsorption on the 3Ni-In sites and dissociated CO 2 adsorption on 3Ni-C sites on the InNi 3 C 0.5 (111) plane ( 23 ). The InNi 3 C 0.5 /SiO 2 and InNi 3 C 0.5 / a -ZrO 2 catalysts also offer two CO 2 desorption peaks at 500°C (with trace CO) and 635°C (with comparable CO amount) ( Fig.…”

“…This linear adsorption of CO is also observed on the InNi 3 C 0.5 /ZrO 2 catalysts but exhibits a visible red shift from 2077 to 2075 (InNi 3 C 0.5 /a-ZrO ZrO 2 ) and unsupported InNi 3 C 0.5 as references. The supports desorb little CO 2 , showing the poor ability to adsorb CO 2 , while the unsupported InNi 3 C 0.5 desorbs a huge amount of CO 2 at 510°C (with trace CO) and 637°C (concomitantly with abundant CO; Fig.3D), respectively assigned to the nondissociated CO 2 adsorption on the 3Ni-In sites and dissociated CO 2 adsorption on 3Ni-C sites on the InNi 3 C 0.5 (111) plane(23). The InNi 3 C 0.5 /SiO 2 and InNi 3 C 0.5 /a-ZrO 2 catalysts also offer two CO Notably, little CO 2 is desorbed below 500°C for these four catalysts, indicating the poor ability to adsorb CO 2 on supports even after loading InNi 3 C 0.5 .…”

First-principles study of the surface structure and stability of BC5

“…The surface structure and properties is of great importance for various applications, such as catalysis and growth of nanoparticle [29][30][31][32]. For all considered low-index surfaces, we first identify the most stable termination of each surface.…”

Oxidative Dehydrogenation of Ethane: Superior Nb2O5-NiO/Ni-Foam Catalyst Tailored by Tuning Morphology of NiO-Precursors Grown on a Ni-Foam

“…Despite the above-mentioned interesting advances, the real-world use of these catalysts still remains a challenge as their poor thermal conductivity is detrimental to rapid dissipation of reaction heat released in this strongly exothermic ODE reaction (ΔH = −104 kJ mol −1 ), which causes severe hotspots in the catalyst bed and therefore leads to the ethylene excessive oxidation while releasing more heat. Recently, the development of structured catalyst based on the monolithic metal-foam has been attracting great interest in heterogeneous catalysis because of the intensified heat transfer, which is favorable to tailor catalysts for strongly exothermic reactions (Chen et al., 2019, Zhao et al., 2016, Zhang et al., 2018a, Zhang et al., 2018b). However, the main issue is how to make these promising metal-foam qualified catalysts, or more concretely, how to fabricate the highly active and selective NiO-based nanocomposites onto foam surface.…”