Coordination environment dependent selectivity of single-site-Cu enriched crystalline porous catalysts in CO2 reduction to CH4

The electrochemical CO2 reduction to high-value-added chemicals is one of the most promising and challenging research in the energy conversion field. An efficient ECR catalyst based on a Cu-based conductive metal-organic framework (Cu-DBC) is dedicated to producing CH4 with superior activity and selectivity, showing a Faradaic efficiency of CH4 as high as ~80% and a large current density of −203 mA cm−2 at −0.9 V vs. RHE. The further investigation based on theoretical calculations and experimental results indicates the Cu-DBC with oxygen-coordinated Cu sites exhibits higher selectivity and activity over the other two crystalline ECR catalysts with nitrogen-coordinated Cu sites due to the lower energy barriers of Cu-O4 sites during ECR process. This work unravels the strong dependence of ECR selectivity on the Cu site coordination environment in crystalline porous catalysts, and provides a platform for constructing highly selective ECR catalysts.

Approximations for the Concentration and Effectiveness Factor in Porous Catalysts of Arbitrary Shape: Taylor Series and Akbari-Ganji’s Methods

A mathematical model of reaction-diffusion problem with Michaelis-Menten kinetics in catalyst particles of arbitrary shape is investigated. Analytical expressions of the concentration of substrates are derived as functions of the Thiele modulus, the modified Sherwood number, and the Michaelis constant. A Taylor series approach and the Akbari-Ganji's method are utilized to determine the substrate concentration and the effectiveness factor. The effects of the shape factor on the concentration profiles and the effectiveness factor are discussed. In addition to their simple implementations, the proposed analytical approaches are reliable and highly accurate, as it will be shown when compared with numerical simulations.

Dual functioning porous catalysts: Robust electro-oxidation of small organic molecules and water electrolysis at bimetallic Ni/Cu foam

In this work, we report a single-step preparation of porous Ni-based foams thin layer atop Cu substrate via a facile dynamic hydrogen bubble template technique (DHBT). The prepared porous Ni-based...

Accurately manipulating hierarchical flower-like Fe2P@CoP@nitrogen-doped carbon spheres as an efficient carrier material of Pt-based catalyst

Fabrication of hierarchical porous catalysts with large specific surface area and tunable architecture provides an effective strategy to promote the catalytic performance of Pt-based catalysts. Herein, we design and construct...

PMO12@ZIF-8/ZnO Derived Hierarchical Porous Molybdenum Carbide as Efficient Electrocatalysts for Hydrogen Evolution

It is significant to design porous catalysts with increased active surface and revealed more catalytic sites for improving catalytic performance. In this paper, MoC@NC is synthesized via a one-step carbonization...

Enhanced carbon dioxide conversion at ambient conditions via a pore enrichment effect

Chemical fixation of carbon dioxide (CO2) may be a pathway to retard the current trend of rapid global warming. However, the current economic cost of chemical fixation remains high because the chemical fixation of CO2 usually requires high temperature or high pressure. The rational design of an efficient catalyst that works at ambient conditions might substantially reduce the economic cost of fixation. Here, we report the rational design of covalent organic frameworks (COFs) as efficient CO2 fixation catalysts under ambient conditions based on the finding of “pore enrichment”, which is concluded by a detailed investigation of the 10994 COFs. The best predicted COF, Zn-Salen-COF-SDU113, is synthesized, and its efficient catalytic performance for CO2 cycloaddition to terminal epoxide is confirmed with a yield of 98.2% and turnover number (TON) of 3068.9 under ambient conditions, which is comparable to the reported leading catalysts. Moreover, this COF achieves the cycloaddition of CO2 to 2,3-epoxybutane under ambient conditions among all porous materials. This work provides a strategy for designing porous catalysts in the economic fixation of carbon dioxide.

Operando detection of single nanoparticle activity dynamics inside a model pore catalyst material

Nanoconfinement in porous catalysts may induce reactant concentration gradients inside the pores due to local conversion. This leads to inefficient active material use since parts of the catalyst may be trapped in an inactive state. Experimentally, these effects remain unstudied due to material complexity and required high spatial resolution. Here, we have nanofabricated quasi–two-dimensional mimics of porous catalysts, which combine the traits of nanofluidics with single particle plasmonics and online mass spectrometry readout. Enabled by single particle resolution at operando conditions during CO oxidation over a Cu model catalyst, we directly visualize reactant concentration gradient formation due to conversion on single Cu nanoparticles inside the “model pore” and how it dynamically controls oxidation state—and, thus, activity—of particles downstream. Our results provide a general framework for single particle catalysis in the gas phase and highlight the importance of single particle approaches for the understanding of complex catalyst materials.