The docs for RealityKit include the structs: OcclusionMaterial, SimpleMaterial, and UnlitMaterial for adding materials to a ModelEntity.
Alternatively you can load in a model with a material attached to it.
I want to add a custom material/texture to a ModelEntity programmatically. How can I achieve this on the fly without adding the material to a model in Reality Composer or some other 3D Software?
Updated: June 14, 2022
There are 6 types of materials in RealityKit 2.0 and RealityFoundation at the moment:
To apply these materials use the following logic:
import Cocoa
import RealityKit
class ViewController: NSViewController {        
    @IBOutlet var arView: ARView!
    
    override func awakeFromNib() {
        let box = try! Experience.loadBox()
        
        var simpleMat = SimpleMaterial()
        simpleMat.color = .init(tint: .blue, texture: nil)
        simpleMat.metallic = .init(floatLiteral: 0.7)
        simpleMat.roughness = .init(floatLiteral: 0.2)
        
        var pbr = PhysicallyBasedMaterial()
        pbr.baseColor = .init(tint: .green, texture: nil) 
        let mesh: MeshResource = .generateBox(width: 0.5, 
                                             height: 0.5, 
                                              depth: 0.5, 
                                       cornerRadius: 0.02, 
                                         splitFaces: true)
        let boxComponent = ModelComponent(mesh: mesh,
                                     materials: [simpleMat, pbr])
        box.steelBox?.children[0].components.set(boxComponent)
        box.steelBox?.orientation = Transform(pitch: .pi/4, 
                                                yaw: .pi/4, 
                                               roll: 0).rotation
        arView.scene.anchors.append(box)
    }
}

Read this post to find out how to load a texture for RealityKit's shaders.
We know that in SceneKit there are 5 different shading models, so we can use RealityKit's SimpleMaterial, PhysicallyBasedMaterial and UnlitMaterial to generate all these five shaders that we've been accustomed to.
Let's see how it looks like:
SCNMaterial.LightingModel.blinn           – SimpleMaterial(color: . gray,
                                                        roughness: .float(0.5),
                                                       isMetallic: false)
SCNMaterial.LightingModel.lambert         – SimpleMaterial(color: . gray,
                                                        roughness: .float(1.0),
                                                       isMetallic: false)
  
SCNMaterial.LightingModel.phong           – SimpleMaterial(color: . gray,
                                                        roughness: .float(0.0),
                                                       isMetallic: false)
SCNMaterial.LightingModel.physicallyBased – PhysicallyBasedMaterial()
// all three shaders (`.constant`, `UnlitMaterial` and `VideoMaterial `) 
// don't depend on lighting
SCNMaterial.LightingModel.constant        – UnlitMaterial(color: .gray)
                                          – VideoMaterial(avPlayer: avPlayer)
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