Synergistic Integration of Zr-MOF (UiO-66) and Bi Electrocatalysts for Enhanced CO2 Conversion to Formate
Authors: Song Jun Tae , Takaoka Yuta , Takagaki Atsushi , Watanabe Motonori , Ishihara Tatsumi 
Published: February 2024

The utilization of renewable energy-driven CO2 conversion technology has garnered considerable attention as a potential remedy for both the energy crisis and climate change. Among various methods, the electrocatalytic CO2 reduction reaction (CO2RR) has received particular focus due to its mild reaction conditions and its ability to produce various valuable products. Specifically, formic acid holds great promise for CO2 electrolysis due to its potential for energy storage and transportation, as well as its commercial viability as indicated by techno-economic assessments. Bi, In, and Sn are several metal catalysts that have been reported for formic acid production, with Bi catalysts demonstrating favorable properties in terms of both cost-effectiveness and selective production of formic acid. However, despite efforts to enhance the intrinsic catalytic activity of Bi through methods such as nanostructuring and alloying, it has yet to achieve the desired level of performance. In light of recent findings by Nam et al. on the ability of a metal-organic framework (MOF) to regulate reaction intermediates for Ag catalyst, resulting in higher CO production, we draw inspiration from MOF's versatility and demonstrate the successful coupling of Bi with UiO-66, a Zr-MOF, to achieve higher CO2 reduction rates and thus increase formic acid production [1].
We synthesized MOF materials, UiO-66 and NH2-functionalized UiO-66 (UiO-66-NH2), and deposited Bi catalysts on the MOF structures using the NaBH4 reduction method, resulting in Bi/UiO-66 and Bi/UiO-66-NH2 samples. To compare the catalytic activity, we also synthesized Bi particle samples using the same method (Bi). Prior to CO2 reduction examination, all electrocatalysts were pre-treated in a 1.0 M KOH solution for 5 minutes, and then CO2 electrolysis was performed in a flow-cell reactor. Among the synthesized samples, Bi/UiO-66 demonstrated excellent CO2 reduction properties, exhibiting about 5 times higher current density (-220 mA/cm2) at an applied potential of -0.7 V vs. the reversible hydrogen electrode (RHE) than Bi alone (-44 mA/cm2), despite the identical electrochemically active surface area (ECSA) for both samples. On the other hand, Bi/UiO-66-NH2 showed an almost identical ECSA-normalized current density compared to Bi/UiO-66, indicating the negligible effect of NH2 functionalization on UiO-66 for CO2RR. Nevertheless, it is evident that the utilization of Zr-MOF (UiO-66) is beneficial in increasing the CO2 conversion rate of metallic Bi catalyst. To comprehend the reason behind the superior catalytic activity exhibited by the Bi/UiO-66 sample, we conducted various characterizations, such as SEM, TEM, FTIR, Raman, and XPS. Our results revealed that the structural evolution of UiO-66 occurs by the formation of carbonate-coordinated Zr-hydroxide during CO2 electrolysis, contributing to the high CO2 reduction current density. Moreover, the disappearance of the carbonate-relevant peak in the C 1s from XPS analysis after the decline in catalytic activity suggests that the carbonate species formed at Zr-MOF site, which is the captured form of CO2 molecules, play a crucial role in efficient CO2 capture and conversion. These findings suggest that Zr-MOF can be used for CO2 capture and conversion with high efficiency.
[1] Nam et al., J. Am. Chem. Soc. 2020, 142, 51, 21513–21521.