High-performance light-driven heterogeneous CO2 catalysis with near-unity selectivity on metal phosphides

Abstract

Akin to single-site homogeneous catalysis, a long sought-after goal is to achieve reaction site precision in heterogeneous catalysis for chemical control over patterns of activity, selectivity and stability. Herein, we report on metal phosphides as a class of material capable of realizing these attributes and unlock their potential in solar-driven CO2 hydrogenation. Selected as an archetype, Ni12P5 affords a structure based upon highly dispersed nickel nanoclusters integrated into a phosphorus lattice that harvest light intensely across the entire solar spectral range. Motivated by its panchromatic absorption and unique linearly bonded nickel-carbonyl-dominated reaction route, Ni12P5 is found to be a photothermal catalyst for the reverse water gas shift reaction, offering a CO production rate of 960 ± 12 mmol gcat−1 h−1, near 100% selectivity and long-term stability. Successful extension of this idea to Co2P analogs implies that metal phosphide materials are poised as a universal platform for high-rate and highly selective photothermal CO2 catalysis.

Chromatic Fulleropyrrolidine as Long‐Lived Metal‐Free Catalyst for CO2 Photoreduction Reaction

“…Due to the poison of surface reactive sites, the activity of common catalysts degrades with increasing reaction time. [36,37] To date, most catalytic systems for the photoreduction of CO 2 can only operate steadily over periods of several to several tens of h, [4][5][6] and only few catalysts reach around 100 h stability, [16,38] significantly impeding the commercialization of existing catalysts. Herein, the long-term stability of the catalyst was evaluated by comparing NMR, UV/ Vis absorption, and Fourier-transform infrared (FTIR) spectra (Figure S9) of the fresh and the used DTBT-C 60 .…”

A core-shell catalyst design boosts the performance of photothermal reverse water gas shift catalysis

“…For comparison studies, two silica-supported Ni 12 P 5 nanoparticles with the loading of 8 wt% and 15 wt%, denoted as SP-1 and SP-2, respectively, were prepared through the wetness impregnation method adapted from [45]. Fig.…”

“…Ni 12 P 5 nanoparticles were prepared through the same method reported in our previous study [45]. In a typical synthesis, nickel nitrate and (NH 4 ) 2 HPO 4 with the molar ratio of 12:5 were first dissolved in deionized water to form the precursor solution.…”

“…A few catalysts exhibited very high CO selectivity in photothermal CO 2 catalysis but still suffered from poor activity and/or stability [39][40][41][42][43][44]. Very recently, we discovered that transition metal phosphide (such as Ni 12 P 5 ) nanoparticles supported on silica could catalyze the photothermal RWGS reaction with a robust near-unity CO selectivity [45]. Nevertheless, the performance of Ni 12 P 5 in photothermal RWGS catalysis is still limited by the trade-off between the catalyst loading and dispersity.…”

Recent Progress on Photothermal Heterogeneous Catalysts for CO2 Conversion Reactions

“…As expected, the supported 10.4 wt% Ni 12 P 5 /SiO 2 catalyst recorded a %5-fold-enhanced CO production rate than Ni 12 P 5 , reaching %960 mmol g À1 h À1 . [44] Further encapsulating Ni 12 P 5 into the SiO 2 shell not only increased the loading of Ni 12 P 5 up to %30 wt%, without sacrificing its dispersity, but also improved its efficiency and stability in photothermal RWGS. [45] 3.1.2.…”