Hydrogen is an attractive, clean, sustainable energy source primarily produced via industry. At present, most reviews on hydrogen mainly focus on the preparation and storage of hydrogen, while the development and utilization of natural hydrogen will greatly reduce its cost. Natural hydrogen has been discovered in many geological environments. Therefore, based on extensive literature research, in this study, the distribution and sources of natural hydrogen were systematically sorted, and the identification method and occurrence state of natural hydrogen were examined and summarized. The results of this research show that hydrogen has been discovered in oceanic spreading centers, transform faults, passive margins, convergent margins, and intraplate settings. The primary sources of the hydrogen include alterations in Fe(II)-containing rocks, the radiolysis of water, degassed magma, and the reaction of water- and silica-containing rocks during the mechanical fracturing. Hydrogen can appear in free gas, it can be adsorbed and trapped in inclusions. Currently, natural hydrogen exploration is in its infancy. This systematic review helps to understand the origin, distribution, and occurrence pattern of natural hydrogen. In addition, it facilitates the exploration and development of natural hydrogen deposits, thus enabling the production of low-cost hydrogen.

The paper adopts an interdisciplinary approach to comprehensively review the current knowledge in the field of porous geological materials for hydrogen adsorption. It focuses on detailed analyses of the adsorption characteristics of hydrogen in clay minerals, shale, and coal, considering the effect of factors such as pore structure and competitive adsorption with multiple gases. The fundamental principles underlying physically controlled hydrogen storage mechanisms in these porous matrices are explored. The findings show that the adsorption of hydrogen in clay minerals, shale, and coal is predominantly governed by physical adsorption that follows the Langmuir adsorption equation. The adsorption capacity decreases with increasing temperature and increases with increasing pressure. The presence of carbon dioxide and methane affects the adsorption of hydrogen. Pore characteristics—including specific surface area, micropore volume, and pore size—in clay minerals, shale, and coal are crucial factors that influence the adsorption capacity of hydrogen. Micropores play a significant role, allowing hydrogen molecules to interact with multiple pore walls, leading to increased adsorption enthalpy. This comprehensive review provides insights into the hydrogen storage potential of porous geological materials, laying the groundwork for further research and the development of efficient and sustainable hydrogen storage solutions.

The present study investigates the adsorption of hydrogen gas by the Triassic Chang 7 Shale Member in the Ordos Basin, China. The mineral composition, microscopic morphology, pore characteristics, hydrogen adsorption capacity, and factors influencing hydrogen adsorption were explored using X-ray diffraction (XRD), thin section observations, nitrogen adsorption, scanning electron microscopy (SEM), and high-pressure hydrogen adsorption experiments. Based on these integrated tools, it was revealed that the Chang 7 Shale Member primarily comprises organic matter (kerogen) and clay minerals (predominantly an illite/smectite-mixed layer [I/S]). Nitrogen adsorption–desorption curves indicated the presence of slit-shaped pores, cracks, and wedge-shaped structures. The adsorption of hydrogen by shale decreases with increasing temperature and increases with increasing pressure. This adsorption behaviour conforms to both the Freundlich and Langmuir equations; moreover, the Freundlich equation provides a better fit. Organic matter (kerogen) and clay minerals considerably influence hydrogen adsorption. The present research provides insights into the occurrence of hydrogen in shale, offering implications for the exploration of natural hydrogen gas.

The complexity of the pore system hindered our understanding of the storage and transport properties of organic-rich shales, which in turn brought challenges to the efficient exploration and development of shale oil and gas. This study, based on elemental, mineralogical, petrographic, and petrophysical approaches, attempts to reveal the pore structure and fractal characteristics of a suite of Permian shales collected from the northeastern Sichuan Basin, China. The results showed that meso-pores make up the main proportion of the total pore volume in the Permian shale in this study; most of the pore size distribution patterns for micro pores and meso-macropores are bimodal. Pores related to clay minerals, organic matter pores, and intragranular dissolution pores are the main storage spaces in these shales. In these samples, ink-bottle pores dominate, with some slit and wedge-shaped ones developed. The morphology of the pores in the studied shales is mainly ink-bottle pores, with some slit-shaped and wedge-shaped pores. The fractal dimension D₂ is greater than D₁, indicating that the homogeneity of pore space is stronger than that of the specific surface area. Quartz in Permian shales inhibits the development of macro- and mesopore spaces and enhances pore heterogeneity, while clay minerals facilitate the development of macro- and mesopore spaces and attenuate pore heterogeneity. The organic matter content shows a negative impact on the macropore volume due to the stripped occurrence and matrix filling. This study has a vital significance for current exploration and development of shale gas in Permian strata in the Sichuan Basin and offers insights for Permian shales in other basins all over the world.