Construction of Ni/In2O3 Integrated Nanocatalysts Based on MIL-68(In) Precursors for Efficient CO2 Hydrogenation to Methanol

Jul 6, 2026

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Efficient and economic conversion of CO2 and renewable H2 into methanol addresses growing anthropogenic CO2 emissions. A preparation strategy for Ni/In2O3 nanocatalysts uses porous MIL-68(In) and Ni(acac)2 as dual precursors of In2O3 and Ni, enabling well-dispersed ~6.2 nm Ni nanoparticles on a porous In2O3 support while suppressing sintering at high temperature. With 5 wt% Ni, catalytic performance surpasses an In(OH)3-derived comparator, maintaining durability for 120 h, whereas high Ni loading promotes Ni–In alloy formation and elevated CO selectivity. In situ spectroscopy and DFT indicate a formate pathway to methanol via HCOO* and *H3CO intermediates.

LanguageEnglish

CategoryResearch & Report

FormatPDF

Pages17

Reading Time43 min

Introduction

CO2-to-methanol conversion strategies

Role of heterogeneous catalysts and In2O3

Supported M/In2O3 catalysts and Ni relevance

[www.acsami.org](www.acsami.org) Research Article Construction of Ni/In2O3 Integrated Nanocatalysts Based on MIL- 68(In) Precursors for Efficient CO2 Hydrogenation to Methanol Yiling Wu,∥ Kaiji Xu,∥ Jian Tian, Longmei Shang, Kok Bing Tan, Hao Sun, * Kang Sun, Xiaoping Rao,* and Guowu Zhan * Cite This: ACS Appl. Mater. Interfaces 2024, 16, 16186−16202 Read Online Downloaded via IISER MOHALI on July 6, 2026 at 04:36:08 (UTC) . See [https://pubs.acs.org/sharingguidelines](https://pubs.acs.org/sharingguidelines) for options on how to legitimately share published articles. ACCESS Metrics & More Article Recommendations *sı Supporting Information ABSTRACT: The efficient and economic conversion of CO2 and renewable H2 into methanol has received intensive attention due to growing concern for anthropogenic CO2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In2O3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac)2) as the dual precursors of In2O3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed th the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles ( 6.2 nm) on the porous In2O3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In2O3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH)3 as a precursor of In2O3. The obtained Ni/In2O3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In2O3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid ofin situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In2O3 catalyst predominantly follows the formate pathway in the CO2 hydrogenation to methanol, with HCOO* and *H3CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In2O3 nanocatalyst fabricated using metal−organic frameworks as precursors can effectively promote CO2 thermal hydrogenation to methanol. KEYWORDS: CO2 hydrogenation, methanol, Ni catalyst, In2O3, MOFs 1. INTRODUCTION The atmospheric concentration of carbon dioxide (CO2) continues to rise as a result of human activities, causing serious climate change, ocean acidification, and other related environmental problems.1 Therefore, the efficient conversion of CO2 into value-added chemicals and fuels has drawn tremendous research attention. Methanol (CH3 OH) is particularly attractive in the context of sustainable development as a precursor of various hydrocarbons and chemicals or even as a fuel itself.2,3 Currently, three main strategies have been developed for CO2 conversion to produce methanol, including photocatalysis,4,5 electrocatalysis,6−8 and thermal hydrogenation. Among them, CO2 thermal hydrogenation using renewable energy sources or off-peak load H2 is considered a viable, sustainable, and economical path to CO2 utilization.9, 10 There is no doubt that heterogeneous catalysts play a critical role in the conversion of CO2 into methanol due to the thermodynamic stability of the CO2 molecules.11 Indium oxide (In2O3 ), a n-type semiconductor with controllable morphology and a strong redox ability to form oxygen vacancies, exhibits excellent performance in CO2 hydrogenation to methanol, attracting extensive research.12 Besides pure In2 O3 catalysts, many supported M/In2 O3 catalysts (M = Au, 13, 14 Cu,15, 16 Ni,17−22 Pd,23

FAQs

How are Ni/In2O3 nanocatalysts prepared in this study?

Ni/In2O3 nanocatalysts are synthesized using porous MIL-68(In) and Ni(acac)2 as dual precursors, generating In2O3 and Ni components during catalyst fabrication.

What structural effect does MIL-68(In) have on Ni nanoparticles?

Using MIL-68(In) as the precursor promotes good dispersion of Ni nanoparticles (~6.2 nm) on the porous In2O3 support and inhibits metal sintering at high temperatures.

How does Ni loading influence the reaction products during CO2 hydrogenation?

Low-to-moderate Ni loading (5 wt%) improves methanol performance, while high Ni loading (31 wt%) can form Ni–In alloy phases that increase CO formation and CO selectivity up to 69%.

Jul 6, 2026

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