Hydrogenation Activity Research Articles

Vesicle-Shaped Co-Ni-S designed by first principles screening and d-Band center control for active hydrogen evolution

Hydrogen evolution reaction (HER) is considered as an effective pathway for hydrogen production. Herein, to obtain efficient HER catalyst, density functional theory is employed to figure out the optimal candidate for nickel sulfide. Guided by the mechanistic screening, the highly active HER electrocatalyst, Co-substituted Ni3S4, is synthesized by one-step hydrothermal method, resembling a vesicle composed of a broken spherical membrane and encapsulated clusters of nanospheres. Cracks on membrane provide a rational entry for reactant molecules to be enclosed in the vesicle. Additionally, the enhanced intrinsic activity also attributes to the upward shift of the d-band center. From the reaction energy diagrams, the decomposition of H2O* is confirmed as the rate-determining step (RDS) and the energy required for the RDS is efficiently lowered by the elevated d-band center, which made the catalyst achieves 185 mV overpotential at 100 mA·cm−2 and 38 mV at 20 mA·cm−2 lower than utmost Co-Ni-S relative electrocatalyst.

Bimetallic Rex-Ru/C catalyst for fatty acid esters to diesel-range alkanes under low temperature

ABSTRACT The hydrogenation of bio-based oil into biodiesel is a key strategy in reducing reliance on fossil fuels. However, efficient catalysts are needed to enable low-temperature hydrogenation reactions due to the current high-temperature requirement for bio-based oil hydrogenation. Here, bimetallic catalysts Rex-Ru/C for low-temperature hydrogenation of bio-based oils were prepared. The presence of Re oxides (ReOx) in the catalyst enhances the abundance of weak and medium acid sites, thereby facilitating the adsorption of H2. The DFT calculation shows the introduction of Re also improved the adsorption capacity of the catalyst for fatty acid methyl ester and H2. The Re0.25-Ru/C catalyst exhibits superior conversion, selectivity, and recyclability at low temperatures compared to the previously reported catalysts, achieving 100% conversion of methyl stearate with 100% selectivity toward n-heptadecane (C17) and n-octadecane (C18) (reaction conditions: 150°C, 4 h, 2.5 MPa H2). Moreover, the catalyst also shows excellent hydrogenation activity toward various fatty acids or esters, including methyl palmitate, stearic acid, and palmitate at low temperatures. The Re0.25-Ru/C catalyst showed consistent recycling performance over 9 cycles. The decline in catalytic performance of the catalyst was primarily caused by a reduction in ReOx content, resulting in a decrease in acid site concentration. Consequently, there was reduced adsorption of H2 and oil on the catalyst.

Improving the Chemical Utilization Efficiency of Pd Hydrodechlorination Catalysts through Hydrogen-Spillover Empowered Synergy between Pd and TiNiN Support.

The sustainable and affordable environmental application of Pd catalysis needs further improvement of Pd mass activity. Besides the well-recognized importance of physical utilization efficiency─the ratio of surface atoms forming reactant-accessible reactive sites─a lesser-known fact is that the congestion of these reactive sites, which we term as the chemical utilization efficiency, also influences the mass activity. Herein, by leveraging the 100% physical utilization efficiency of a fully exposed Pd cluster (Pdn) and the hydrogenation activity of TiNiN, we developed Pdn/TiNiN as a high physical and chemical utilization efficiency catalyst. During the catalytic hydrodechlorination of 4-chlorophenol and the subsequent hydrogenation of phenol, Pdn focuses on H2 dissociation and C-Cl cleavage, while TiNiN facilitates the subsequent hydrogenation of phenol into less toxic cyclohexanone via H-spillover. This synergy results in a 20-40-fold increase in the hydrodechlorination rate. The enhanced chemical utilization efficiency of Pd informs the design of Pdn/TiNiN microspheres for the conversion of halogenated organics from pharmaceutical wastewater and the design of a fixed-bed reactor to transfer trace amounts of 4-CP from river water. Ultimately, this approach decentralizes the use of Pd in environmental catalysis and reduction processes.

Single-Atom Pt Anchored Polyoxometalate as Electron-Proton Shuttle for Efficient Photoreduction of CO2 to CH4 Catalyzed by NiCo Layered Doubled Hydroxide.

The crucial role of active hydrogen (H*) in photocatalytic CO2 methanation has long been overlooked, although recently, accelerating proton-coupled electron transfer (PCET) processes to enhance CH4 productivity and selectivity has garnered significant attention. Herein, a single-atom Pt-anchored H3PMo12O40 (Pt1-PMo12) is applied as an efficient proton-electron shuttle to facilitate the photocatalytic performance of NiCo layered double hydroxide (NiCo-LDH). The resultant Pt1-PMo12@NiCo-LDH exhibited superior CH4 productivity (723µmolg-1h-1) with CH4 selectivity of 82.3%, showcasing a 24.9 times productivity enhancement over NiCo-LDH (29µmolg-1h-1). Systematic investigations revealed that abundant H* is generated by the dissociation of H2O on Pt1 sites and stored within Pt1-PMo12. Subsequently, the multiple H* rapidly migrated from Pt1-PMo12 to the catalytic sites on NiCo-LDH by the engineered strong Mo─O─Ni/Co bonds, thereby significantly expediting the PCET process. The in situ DRIFTS and theoretical calculations elucidated that the Pt1-PMo12 decreased the energy barrier for *CO protonation to *CHO (0.38-0.18eV) and optimized the rate-determining step of *CH3 to *CH4 (0.64eV), thus promoting highly active and selective CH4 generation. This work provided novel insights into achieving efficient photocatalytic CO2 methanation by modulating the fast generation and transport of active H*.

Synergistic enhancement of catalytic hydrodeoxygenation performance by oxygen vacancies and frustrated Lewis pairs

The catalytic hydrodeoxygenation (CHDO) of lignin into saturated cycloalkanes not only enhances the efficient utilization of lignin but also reduces reliance on high-density liquid fuels (HDLFs), given the importance of saturated cycloalkanes as key constituents of HDLFs. The main challenge in lignin CHDO towards HDLFs is efficiently removing oxygen-atom while maintaining high selectivity for the desired saturated cycloalkanes. Herein, we report for the first time the fabrication of a Ni/N0.8-CeO2-500 composite with abundant oxygen vacancies (OVs) and adjacent frustrated Lewis pairs (FLPs), achieved through the capping effect of ionic liquids. The FLPs of N/Ce3+ within Ni/N0.8-CeO2-500, mediated by OVs, not only enhance the dispersion of Ni species but also effectively facilitate the conversion of H2 into active hydrogen (H*) through relay catalysis involving the Ni species. This integration, combining the oxygen atom-specific recognition of OVs with the adjacent FLPs of N/Ce3+ for the tandem generation of H*, significantly promotes the adsorption/cleavage of Car/alk−O−Calk bonds, oxygen-atom removal, and hydrogenation of aromatic rings, ultimately catalyzing the one-step production of saturated cycloalkanes. The synergistic catalytic interplay results in a remarkable yield of saturated cycloalkanes (up to 88.2 wt%) during the CHDO of Kraft lignin, representing the highest reported value under similar conditions to date. A combination of diverse characterizations, experimental analyses, and kinetic studies collectively reinforces the notion that in-situ N-doping of CeO2 increases the electron cloud density around Ce species, forming N-Ceδ+ entities that, at high temperatures, create OVs and adjacent FLPs of N-Ce3+, collectively enhancing lignin CHDO to yield saturated cycloalkanes.

Intrinsic Activity: A Critical Challenge of Alkaline Hydrogen Oxidation Reaction

AbstractAnion exchange membrane fuel cells (AEMFCs) are advantageous for reducing or even eliminating the dependency on platinum resources, as the alkaline environment allows the use of non‐precious metal catalysts for oxygen reduction reaction at the cathode. However, the intrinsic activity of hydrogen oxidation reaction (HOR) catalysts in alkaline environments is 2 to 4 orders of magnitude lower than in acidic environments, which becomes the major challenge for AEMFCs. This review examines the current developments in the intrinsic activity of alkaline HOR catalysts and systematically summarizes the hydrogen activation mechanism with a focus on potential influencing factors and enhancement strategies. Furthermore, it offers insights into the prospects for developing more efficient alkaline HOR catalysts.

Optimizing Cu 3d Bands with Nanotubular SnO2 to Boost Their Catalytic Transfer Hydrogenation Activity.

Catalytic transfer hydrogenation (CTH) using Cu nanocatalysts offers significant advantages over direct high-pressure hydrogenation. However, the active hydrogen (H*) in this process exhibits poor adsorption and tends to release H2 readily due to the fully occupied 3d states of Cu. To address this issue, a tubular SnO2 support with electron-accepting ability was selected to host Cu nanoparticles, aiming to optimize the Cu 3d bands. The Cu/SnO2 nanohybrids were prepared through an electrospinning technique, followed by hydrothermal synthesis. As evidenced by X-ray photoelectron spectroscopy (XPS) binding energy shifts and density functional theory (DFT) simulations, some electrons from Cu transferred to SnO2 in the Cu/SnO2 nanohybrids due to their different work functions. Such electron transfer enables the Cu 3d orbitals to lose electrons and alters its valence configuration from 3d10 to 3d10-x, which enhances the adsorption of active H* atoms and thereby inhibits undesirable H2 release. The 15 wt % Cu/SnO2 exhibits improved catalytic hydrogenation of 4-nitrophenol with NaBH4, with an optimal normalized rate constant of 56.98 mg-1 min-1 and a turnover frequency of 4.82 min-1, surpassing most reported catalysts. The enhanced activity is attributed to the optimized electronic states, improved hydrogen adsorption, and the tubular structure of the support. This work might shed light on developing more non-noble metal nanocatalysts for CTH by tuning their d bands with appropriate oxide supports.

The investigation of highly efficient chlorinated hydrocarbons removal based on metal nanoparticles carbonaceous synthetic particles: The degradation behavior and selective transformation mechanism

Overconsumption in industrial manufacturing has led to critical emissions of chloroalkanes, posing a significant environmental threat. In this study, the innovative biochar (BC) particles containing nanocrystalline: NZVI, Fe/Pd, Fe/Ni were prepared by impregnation-liquid phase reduction using the pyrolysis of coconut husk as precursors to explore the degradation capabilities of chloroform (CF) via orthogonal experiment. The results indicated that when the pH value was 3, the temperature was 20 ℃, and the reaction time was 60 min, the CF removal efficiency of Fe/Ni-BC reached 80.38 ± 2.08 %, outperforming all other tested synthetic particles. Advanced characterization techniques showed that the abundant dispersed metallic nanoparticle sites would refresh the surface crystal morphology, improve the adsorption enrichment ability of biochar, enhance electron transfer capacity of synthetic particles, and further participate in reductive dechlorination by inducing an electrophilic attack of active hydrogen. Theoretical calculations verified that hydrogen activation and CF facile adsorption would be easily achieved after the introduction of metal nanoparticles, profiting from the multiple synergistic effects between special π-delocalized bond of biochar in carbon layer and multiple nanoparticles docking sites, and thus enhancing the specific CF catalytic selectivity of Fe/Ni as the active center. Collectively, the CF degradation on Fe/Ni-BC was a complex chemisorption process along with reductive hydrogenation decomposition, which achieved the parent CF reduction and promoted the conversion of the low-chlorinated benign products. These findings offer new insights into the developed multifunctional BC and their comprehensive assessment of CF sewage remediation.

Butadiene hydrogenation on N-doped carbon-hosted non-noble metal nanostructures

Diverse N-doped carbon-supported non-noble metal nanostructures (Ni, Co, Fe, Cu) are designed, and explored in selective butadiene hydrogenation. Focusing on particle size and composition, optimal catalytic performance is observed with Ni catalysts, where smaller metallic Ni particles of ca. 6.2 nm exhibit superior activity and larger ones (14–47 nm) display much higher total butene selectivity. An integral approach combining detailed kinetics, chemisorption, and dual-beam Fourier transform infrared spectroscopic study is performed to rationalize the Ni particle size effect. The findings reveal that smaller Ni particles offer improved activation of butadiene and hydrogen due to advantageous adsorption dynamics. Spectroscopic examinations further suggest different adsorption configurations existing on Ni particles, with larger particles displaying strong π-adsorption, which impedes hydrogen replacement. Additionally, the stability of the catalysts is scrutinized under various reaction conditions, revealing that deactivation occurs more rapidly at lower temperatures, primarily due to mild coke deposition.

Selective hydrogenation of 1,3-butadiene to butenes on ceria-supported Pd, Ni and PdNi catalysts: Combined experimental and DFT outlook

The regulation of catalyst activity and selectivity using a reducible support for the industrially relevant hydrogenation of 1,3-butadiene to more valuable butene products was achieved. Supported palladium and nickel–palladium catalysts on ceria were prepared and characterized with hydrogen temperature programmed reduction (H2-TPR), hydrogen temperature programmed desorption (H2-TPD), X-ray photoelectron spectroscopy (XPS), high resolution transmission electron microscopy (HR-TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), temperature programmed oxidation (TPO), energy dispersive spectroscopy (EDS), and N2 adsorption–desorption to examine their chemical and physical properties. Pathways guiding the reaction were determined using the density functional theory (DFT). H2-TPR confirmed that palladium oxide was reduced, and nickel oxide species strongly interacted with the CeO2 support. The Ce3+ concentration determined by XPS showed that all catalysts surface contained the Ce reduced state. The catalysts showed a similar BET surface area, with 4Pd–Ce presenting the lowest value due to particle aggregation, which was confirmed from the EDS mapping analysis. Butadiene conversion consistently increased with temperature (40 °C–120 °C) until full conversion was reached on all the Pd catalysts while the maximum conversion on the 4Ni-Ce catalyst was 88 % at 120 °C. Product distribution revealed that 4 % Pd content directed the products toward butane when 40 °C was exceeded. Constructed mechanisms by DFT calculations featured low reaction barriers for the involved surface hydrogenation steps, and thus, they accounted for the observed low temperature of the surface hydrogenation activity. Selective formation of 1-butene partially stemmed from its relatively weak binding to Ni sites in reference to Pd sites. The mapped-out mechanisms entailed a higher reaction barrier for the formation of 2-butene, in agreement with the experimental observation pertinent to its formation at higher temperatures when compared with that of 1-butene.

Amorphous Ni3B Promotes Electroreduction of Nitrate to Ammonia.

The electrocatalytic nitrate reduction to ammonia (NRA) can address nitrogen cycle imbalance and high carbon emissions; however, the intense competition of hydrogen evolution reaction (HER) restricts the rate of NH3 production. Herein, amorphous Ni3B (a-Ni3B) is designed to balance the NRA and HER. The NH3 yield of a-Ni3B surpasses those of pure Ni and NiO, which is attributed to the preferential adsorption of NO3- on the B and Ni sites of a-Ni3B for the NRA reaction, greatly inhibiting the HER. Furthermore, the a-Ni3B possesses advantages in NRA performance compared to crystalline Ni3B (c-Ni3B) due to more active hydrogen (*H) generated during the catalytic process. The *H in the NRA process on a-Ni3B is verified by the electron spin resonance technique. The NRA mechanism is comprehensively discussed based on the results of in situ characterization and density functional theory calculations. The a-Ni3B can enhance NH3 production by inhibiting HER, which provides ideas for sustainable NH3 synthesis.

Preparation and Catalytic Properties of Gold Single-Atom and Cluster Catalysts Utilizing Nanoparticulate Mg-Al Layered Double Hydroxides.

Au single atoms and clusters were stabilized on Mg-Al layered double hydroxide nanoparticles (LDH NPs), and the obtained Au@LDH NPs were supported on SiO2 and CeO2. After hydrogen reduction, Au single atoms were found together with Au clusters on LDH/SiO2. In contrast to Au single-atom catalysts which are deposited in metal vacancies of oxide supports, the LDH NPs stabilize very small Au species despite the absence of metal vacancies. The obtained Au(0)@LDH/SiO2 catalyzed aerobic oxidation of alcohols, and Au single atoms maintained after the reaction. Given that only Au NPs were observed on bulk LDH, the abundant surface OH group of LDH NPs would contribute to stabilize Au, resulting in higher activity than Au/LDH-bulk. After calcination to transform LDH to mixed metal oxide (MMO), the obtained Au(0)@MMO/SiO2 also exhibited high catalytic activity. Moreover, Au(0)@LDH/CeO2 exhibited higher activity and excellent selectivity for hydrogenation of 4-nitrostyrene to 4-aminostyrene than conventional Au catalysts such as Au/CeO2 and Au/TiO2. We demonstrated that Au size can be minimized using LDH NPs, exhibiting high catalytic performance. The basic surface OH groups of LDH would be also beneficial for deprotonation of alcohols and heterolytic dissociation of H2 in the catalytic reactions.

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide‐to‐Methanol Conversion

AbstractZnO/ZrO2 catalysts have shown better activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalysts supported on tetragonal ZrO2 (ZnO/ZrO2‐t) and monoclinic ZrO2 (ZnO/ZrO2‐m), which resulted in the formation of different ZnOx species, consisting of sub‐nanometer ZnO moieties and large‐sized ZnO particles, respectively. ZnO/ZrO2‐t exhibited a higher methanol selectivity (81 vs. 39 %) and methanol yield (1.25 vs. 0.67 mmol g−1 h−1) compared with ZnO/ZrO2‐m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO2‐t had a high density of ZnOx‐ZrOy sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO2‐t during catalysis, while larger ZnO particles on ZnO/ZrO2‐m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.

Highly Dispersed ZnO Sites in a ZnO/ZrO2 Catalyst Promote Carbon Dioxide-to-Methanol Conversion.

ZnO/ZrO2 catalysts have shown better activity in the CO2 hydrogenation to methanol compared with single component counterparts, but the interaction between ZnO and ZrO2 is still poorly understood. In particular, the effect of the ZrO2 support phase (tetragonal vs. monoclinic) was not systematically explored. Here, we have synthesized ZnO/ZrO2 catalysts supported on tetragonal ZrO2 (ZnO/ZrO2-t) and monoclinic ZrO2 (ZnO/ZrO2-m), which resulted in the formation of different ZnOx species, consisting of sub-nanometer ZnO moieties and large-sized ZnO particles, respectively. ZnO/ZrO2-t exhibited a higher methanol selectivity (81 vs. 39 %) and methanol yield (1.25 vs. 0.67 mmol g-1 h-1) compared with ZnO/ZrO2-m. The difference in performance was attributed to the redox state and degree of dispersion of Zn, based on spectroscopy and microscopy results. ZnO/ZrO2-t had a high density of ZnOx-ZrOy sites, which favored the formation of active HCOO* species and enhanced the yield and selectivity of methanol along the formate pathway. Such ZnO clusters were further dispersed on ZrO2-t during catalysis, while larger ZnO particles on ZnO/ZrO2-m remained stable throughout the reaction. This study shows that the phase of ZrO2 supports can be used to control the dispersion of ZnO and the catalyst surface chemistry, and lead to enhanced catalytic performance.

CoZnyB/Nb2CTx(MXene) for cinnamaldehyde hydrogenation to cinnamyl alcohol: Effects of Zn

Amorphous cobalt boride (CoB) catalysts have superior CO selectivity for cinnamaldehyde (CAL) hydrogenation and low activity. This work prepared CoZnyB/Nb2CTx(MXene) catalysts with different Zn ratios (y=0, 0.025, 0.05, 0.075, and 0.1) via a wet reduction method, which were subsequently utilized in the selective hydrogenation of CAL to cinnamyl alcohol (COL). The CoZn0.05B/Nb2CTx catalyst exhibited superior low-temperature activity, with 91.4 % CAL conversion and a 66.3 % COL yield. SEM and XPS analyses further revealed that Zn enhanced the catalytic activity by generating smaller amorphous alloy particles and exposing more Co0 active sites. Furthermore, the NH3-TPD and adsorbed pyridine DRIFTS results showed that Zn modified the surface acidity of the CoZnyB/Nb2CTx catalyst by generating both Lewis acid sites and Brønsted acid sites, which can facilitate the adsorption of CAL. This work demonstrated that Zn can increase the number of exposed active sites and modify the surface acid properties of amorphous CoB catalysts.

Effect of Calcination Temperature in Large-Aperture Medium-Entropy Oxide (FeCoCuZnNa)O on CO2 Hydrogenation for Light Olefins

The catalytic hydrogenation of carbon dioxide is not only a way to mitigate the greenhouse effect but also provides high-value chemicals. In this work, a medium-entropy oxide catalyst (FeCoCuZnNa)O was prepared by the sol–gel method for highly active and selective hydrogenation of CO2 to value-added hydrocarbons. When reacted at 290 °C, 2.5 MPa, and 2500 mL·gcat−1·h−1, the CO2 conversion and selectivity of olefin were affected by the calcination temperature of the catalyst, and the best performances were 39% and 41.3%. The large pore size and oxygen vacancies (Ov) formed by (FeCoCuZnNa)O promote the activation of CO2 and promote the C-C coupling reaction of Fe5C2 in a hydrogenation reaction. The promoted C-C coupling reaction was related to the surface enrichment of iron species. The presence of Ov also inhibited the excessive hydrogenation reaction, further improving the selectivity of light olefins. In addition, (FeCoCuZnNa)O did not show significant deactivation within 75 h, indicating that the catalyst has strong industrial potential.

Tailoring rhodium-based metal-organic layers for parahydrogen-induced polarization: achieving 20% polarization of 1H in liquid phase

Abstract Heterogeneous catalysts for parahydrogen-induced polarization (HET-PHIP) would be useful for producing high sensitivity contrasting agents for magnetic resonance imaging (MRI) in liquid phase, as they can be removed by simple filtration. Although homogeneous hydrogenation catalysts are highly efficient for PHIP, their sensitivity decreases when anchored on porous supports due to slow substrate diffusion to the active sites and rapid depolarization within the channels. To address this challenge, we explored two-dimensional (2D) metal-organic layers (MOLs) as supports for active Rh complexes with diverse phosphine ligands and tunable hydrogenation activities, taking advantage of accessible active sites and chemical adaptability of the MOLs. By adjusting the electronic properties of phosphines, TPP-MOL-Rh-dppb (TPP = tris(4-carboxylphenyl)phosphine), featuring a κ2-connected di(phosphine) ligand, generated hyperpolarized styrene achieving over 2400-fold signal enhancement and polarization level of 20% for 1H in methanol-d4 solution. The TPP-MOL-Rh-dppb effectively inherited the high efficiency and pairwise addition of its homogenous catalyst while maintaining the heterogeneity of MOL. This work demonstrates the potential of 2D phosphine-functionalized MOLs as heterogenous solid support for HET-PHIP.

Ultrasound-assisted bisphenol AF degradation using in situ generated hydrogen peroxide

Bisphenol AF (BPAF) is degraded through the ultrasound-assisted in situ generation and activation of hydrogen peroxide (H2O2) by the copper(II) catalysed oxidation of hydroxylamine (NH2OH) with dioxygen (O2). Compared to added H2O2, in situ generated H2O2 significantly improves the degradation of BPAF from 46.7% to 94.8% in ∼15 min. The reaction follows a pseudo-first-order kinetic model. This study examines the influence of solution pH, anions, humic acid, and different concentrations of the reactants on BPAF degradation. Mass spectrometry was used to identify the BPAF degradation products, and a degradation pathway is proposed. This work advances the understanding of in situ hydrogen peroxide generation and activation in advanced oxidation (Fenton-like) processes (AOPs).

Change of Hydrogen in Heavy Water and Activation of Unsaturated Fatty Acid by Specially Processed Water

Change of Hydrogen in Heavy Water and Activation of Unsaturated Fatty Acid by Specially Processed Water

Intermetallic Compounds for Hydrogen Storage: Current Status and Future Perspectives.

Intermetallic compounds are an emerging class of materials with intriguing hydrogen activation and storage capabilities garnering attention for their application in low-temperature hydrogen storage and metal hydride batteries. However, none of the existing intermetallic compounds have met the gravimetric hydrogen storage capacity target of 5.5wt.%. Some A2B-type intermetallic compounds, like Mg2Ni, Mg2Co, and Mg2Fe, approach this target but require high temperatures for hydrogen desorption limiting their use in low-temperature hydrogen storage and automotive applications. Conversely, some intermetallic compounds like ZrV2 and LaNi5, exhibit hydrogen desorption at ambient conditions but with comparatively lower hydrogen storage capacities. This review article provides a comprehensive account of the different types of intermetallic compounds, their synthesis using different solidification-based and solid-state diffusion-based approaches, and their metallurgical and structural properties. It examines the complex interdependencies between the structural parameters of intermetallic compounds and hydrogen storage performance. A definitive but non-linear correlation is identified between void volume and gravimetric hydrogen storage capacities while lattice structure, evolution of lattice structure with hydrogen absorption, enthalpy of hydride formation, and hydrogen activation reactivities of intermetallic compounds are identified as critical parameters governing hydrogen storage performance.