The studies of metal phosphides (MPs) have flourished in the past decades due to their exceptional catalytic performance in thermo-, electro-, and photocatalysis. In this review, we summarize the synthesis methods of MPs and attribute their unique catalytic properties to electronic, geometric, and synergetic modifications. The multifunctionality of phosphorus doping makes phosphide an atypical catalyst. The phosphorus withdraws electrons from metal sites, isolates metal sites, and provides synergetic sites simultaneously, leading to high catalytic activities in various reactions, such as hydroformylation, hydrogen evolution reaction (HER), and photocatalytic H2 production. The variety of MPs enables rational design of catalysts based on the requirements of different reactions and expands the application scenarios of MPs. This review summarizes the structure–performance relationship of MPs, paving the way for future catalyst design and mechanism studies. 

Metal Phosphide: An Atypical Catalytic Site

Usually, electrocatalysts depend on pH value for Hydrogen Evolution Reaction (HER) limit their practical application. In this study, NiMo alloys were synthesized on Nickel Foam (NF) using electrodeposition. Furthermore, the proportions of the two metallic elements in the electrolyte, current density and deposition time can affect the catalytic performance. Specifically, the optimized Ni0.8Mo0.8/NF shows highly efficient catalytic performances towards HER in acidic, neutral, alkaline, and seawater. At 100 mA·cm-2, the overpotential values are 111, 366, 158, and 163 mV, respectively. In-situ Raman spectroscopy indicates the presence of multiple active sites during the hydrogen evolution process. Moreover, the Density Functional Theory (DFT) reveals the synergistic effect between the two metals optimizes the material structure, reducing the free energy of H2O and H⁎ adsorption on the catalyst surface in acidic and alkaline environments. This work provides deep insights into designing cost-effective and efficient electrocatalysts towards HER in all-pH-value and alkaline seawater. 

Cooperative Effects between NiMo alloy enable highly efficient for all-pH-value and alkaline seawater hydrogen evolution

As a promising alternative electrocatalyst to platinum for the oxygen reduction reaction (ORR), an Fe-N/C electrocatalyst with more active sites was designed by using N-doped porous crumpled graphene as carbon precursor. More defects provided by the edges and cavities of the porous crumpled graphene facilitated the anchoring and inhibited the growth of Fe clusters, and hence introduced more active sites. Furthermore, crumpled structure combined with the pores provided abundant mass transfer channels, and the fast kinetics were ensured. Consequently, the porous crumpled graphene-based catalyst showed better ORR activity and good electrochemical stability. The half-wave potential (E1/2) of porous crumpled graphene-based catalyst was 0.69 ​V vs. RHE, and the current retention rate was above 97% after 20000s. In addition, the influence of different morphologies, degrees of defect, and compositions on the distribution of active sites and ORR performance of Fe-N/C were systematically studied, and the formation mechanism of Fe-N/C was proposed. This study provided valuable insights into designing more effective non-precious metal based electrocatalysts. 

Defect engineering of Fe–N doped crumpled graphene for improved ORR performance

Introducing defects into Pd-based metallene has been shown to significantly enhance its electrocatalytic performance. In this study, we embedded a new type of atomic-scale cavities into the basal plane of PdMo bimetallene (c-PdMo) through precise etching. These cavities introduced tensile strain and increased the generalized coordination number (CN̅), resulting in superior performance in formate oxidation reaction (FOR) and methanol oxidation reaction (MOR), with mass activities of 5.01 mAμgNM−1 and 5.38 mAμgNM−1, respectively. Notably, a two-electrode system comprising commercial Pt/C and c-PdMo coated on carbon paper achieved cell voltages of only 0.517 V and 0.362 V at 10 mA cm−2 for FOR and MOR, respectively. Additionally, density functional theory calculations revealed that the deliberate lattice tensile strain and enhanced coordination numbers reduced the D-band center of defective PdMo, which improved OH adsorption and reduced CO adsorption, thus optimizing FOR and MOR catalysis on the surface of c-PdMo bimetallene. 

A novel defective PdMo bimetallene with atomic-scale cavities for highly efficient chemicals-assisted hydrogen production

Medium/high-entropy alloy (MEA/HEA) catalysts have emerged as ideal candidates as multi-functional catalysts owing to their synergistic effects of multiple metal components on the boosted catalytic activity. However, the facile preparation and screening of suitable MEAs element to achieve high catalytic performance still remain challenging. In this work, we successfully synthesized a MoCoCu-P MEA electrocatalyst for water splitting electrocatalysis through a feasible electrodeposition method. The as-prepared MEA demonstrated an overpotential of 276.1 mV (j=10 mA/cm²) for OER with a Tafel slope of 38.3 mV/dec, coupled with an overpotential of 64.7 mV for HER (j=10 mA/cm²) with a Tafel slope of 87.7 mV/dec. Employed in an overall water electrolysis cell, MEA achieved a nearly 100% Faradaic efficiency and superior stability over than 50 hours at a high current density of 50 mA/cm2. X-ray photoelectron spectroscopy (XPS) analysis verify that high-valence Co and Mo are the most active sites for OER, while electron-rich Cu at the presence of P is responsible for the boosted HER in the MoCoCu-P MEA. This study not only provides a feasible electrodeposition strategy to obtain MEA catalysts with high activity and excellent stability, but also sheds fundamental lights on the identification of the active sites in MEA catalysis. 

Medium-entropy alloy MoCoCu-P as an efficient bifunctional catalyst for water splitting

Direct formic acid fuel cells (DFAFCs) are considered promising sustainable power sources due to their high energy density, nonflammability, and low fuel crossover. However, serious CO poisoning and activity attenuation of the anodic formic acid oxidation reaction (FAOR) greatly restrict the output and durability of DFAFCs. Inspired by the specific relationship between the composition, type, and property of alloys, in this work, we synthesize a series of hybrid substitutional/interstitial quaternary alloys P-PdAuAg by means of a novel polyphosphide route to address these issues. Due to the simultaneous interstitial P-doping and metal (Au, Ag, Pd) co-reduction, the P-PdAuAg quaternary alloy obtained is only 3 nm in diameter with abundant defects. It not only achieves a new high mass activity of 8.08 A mgPd-1 (6.78 A mgcatalyst-1) but also maintains high stability in the high potential range and harsh reaction conditions. Both the activity and anti-poisoning ability are far exceeding those of the currently reported FAOR catalysts. Detailed density functional theory (DFT) calculations reveal that the superb electrochemical performances originate from the shift of the d-band center of Pd as a result of the synergistic electronic/ligand effects between Pd, Au, Ag, and P. The introduction of interstitial P inhibits the occurrence of an indirect reaction pathway on Pd, while Au and Ag suppress the adsorption of CO and optimize the sequential dehydrogenation steps, leading to boosted reaction kinetics and CO tolerance. This work pioneered a facile way for the synthesis of Pd-based substitutional/interstitial hybrid alloys, providing a promising means of further improving the performance of alloying catalysts.

Boosting the Electrocatalytic Formic Acid Oxidation Activity via P-PdAuAg Quaternary Alloying.

The absence of Pd ensemble sites and weak affinity for O-intermediates in tetracoordinate planar PdN4 sites inhibit O-O bond dissociation and restrict 4e- oxygen reduction reaction (ORR) pathway. Optimizing the adsorption energy between O-intermediates and PdN4 sites is a rational approach for selectively promoting 4e- ORR electrocatalysis. Herein, we propose a molten-salt strategy for introducing axial oxygen ligand into the PdN4 sites to manipulate the electronic structure and create catalytic O-PdN4 sites (one subsurface axial Pd-O configuration on PdN4 plane) on N-doped graphene nanosheets (O-PdN4-NGS). Density functional theory calculations revealed that the axial Pd-O coordination can induce charge redistribution, downshift the d-band center of Pd and enhance the adsorption affinity of PdN4 site for O-intermediates, thereby leading to superior electrocatalysis activity and selectivity for 4e- ORR process compared to conventional PdN4 sites in 0.1 M KOH (with a positive half-wave potential E1/2 of 0.90 V vs RHE). Moreover, zinc-air battery featuring with O-PdN4 sites delivers a peak power density of 178 mW cm−2 at 227.5 mA cm−2 and stable long-term cycling performance, effectively showcasing the advantages of the axial O ligand modification in practical application. This work provides a constructive strategy to activate the reaction activity and specificity of PdN4 single-atom sites by precisely-tuning the local coordination environment of Pd. 

Activating the PdN4 single-atom sites for 4 electron oxygen reduction reaction via axial oxygen ligand modification

Achieving a Record High Activity of 8.08 a Mg-1pd for Electrocatalytic Formic Acid Oxidation Reaction Through P-Pdauag Quaternary Alloying

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Boosting the Electrocatalytic Formic Acid Oxidation Activity via P-PdAuAg Quaternary Alloying.

Activating the PdN4 single-atom sites for 4 electron oxygen reduction reaction via axial oxygen ligand modification

Achieving a Record High Activity of 8.08 a Mg-1pd for Electrocatalytic Formic Acid Oxidation Reaction Through P-Pdauag Quaternary Alloying