Significant progress has been made in direct air capture (DAC) in recent years. Evidence suggests that the large-scale deployment of DAC by adsorption would be technically feasible for gigatons of CO₂ capture annually. However, great efforts in adsorption-based DAC technologies are still required. This review provides an exhaustive description of materials development, adsorbent shaping, in situ characterization, adsorption mechanism simulation, process design, system integration, and techno-economic analysis of adsorption-based DAC over the past five years; and in terms of adsorbent development, affordable DAC adsorbents such as amine-containing porous materials with large CO₂ adsorption capacities, fast kinetics, high selectivity, and long-term stability under ultra-low CO₂ concentration and humid conditions. It is also critically important to develop efficient DAC adsorptive processes. Research and development in structured adsorbents that operate at low-temperature with excellent CO₂ adsorption capacities and kinetics, novel gas–solid contactors with low heat and mass transfer resistances, and energy-efficient regeneration methods using heat, vacuum, and steam purge is needed to commercialize adsorption-based DAC. The synergy between DAC and carbon capture technologies for point sources can help in mitigating climate change effects in the long-term. Further investigations into DAC applications in the aviation, agriculture, energy, and chemical industries are required as well. This work benefits researchers concerned about global energy and environmental issues, and delivers perspective views for further deployment of negative-emission technologies.

This paper reviews recent advances in the shaping adsorbents: alternative geometric forms, key metrics for evaluation, typical steps of main shaping techniques, etc. , are discussed, which can serve as a reference for structured adsorbent design.

Sequential separation-driven steam methane reforming derives low-carbon-footprint H ₂ with >99% conversion (CH ₄ ), yield and selectivity (H ₂ & CO ₂ ) and low energy penalty at 400 °C and 1 bar, and integrates well with solar trough technology.

Supported polyethyleneimine (PEI) adsorbent is one of the most promising commercial direct air capture (DAC) adsorbents with a long research history since 2002. Although great efforts have been input, there are still limited improvements for this material in its CO₂ capacity and adsorption kinetics under ultradilute conditions. Supported PEI also suffers significantly reduced adsorption capacities when working at sub‐ambient temperatures. This study reports that mixing diethanolamine (DEA) into supported PEI can increase 46% and 176% of pseudoequilibrium CO₂ capacities at DAC conditions compared to the supported PEI and DEA, respectively. The mixed DEA/PEI functionalized adsorbents maintain the adsorption capacity at sub‐ambient temperatures of −5 to 25 °C. In comparison, a 55% reduction of CO₂ capacity is observed for supported PEI when the operating temperature decreases from 25 to −5 °C. In addition, the supported mixed DEA/PEI with a ratio of 1:1 also shows fast desorption kinetics at temperatures as low as 70 °C, resulting in maintaining high thermal and chemical stability over 50 DAC cycles with a high average CO₂ working capacity of 1.29 mmol g⁻¹. These findings suggest that the concept of “mixed amine”, widely studied in the solvent system, is also practical to supported amine for DAC applications.